EP1869246A1 - Humidity-regulating composite materials - Google Patents

Humidity-regulating composite materials

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Publication number
EP1869246A1
EP1869246A1 EP06725526A EP06725526A EP1869246A1 EP 1869246 A1 EP1869246 A1 EP 1869246A1 EP 06725526 A EP06725526 A EP 06725526A EP 06725526 A EP06725526 A EP 06725526A EP 1869246 A1 EP1869246 A1 EP 1869246A1
Authority
EP
European Patent Office
Prior art keywords
water
hygroscopic substance
composites
carrier material
monomer
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Withdrawn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
EP06725526A
Other languages
German (de)
French (fr)
Inventor
Dennis LÖSCH
Stefan Bruhns
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1869246A1 publication Critical patent/EP1869246A1/en
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • 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
    • C08J2333/00—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
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2484—Coating or impregnation is water absorbency-increasing or hydrophilicity-increasing or hydrophilicity-imparting

Definitions

  • the present invention relates to moisture-controlling composites, to processes for their preparation and to their use for moisture regulation.
  • Water-absorbing polymers are, in particular, polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives.
  • Such polymers are used as aqueous solution-absorbing products for making diapers, tampons, sanitary napkins and other sanitary articles, but also as water-retaining agents in agricultural horticulture.
  • WO-A-01/56625, EP-A-1 178 149 and US Pat. No. 5,962,068 describe processes for producing water-absorbing composites in which water-absorbing polymers are copolymerized onto a support material.
  • WO-A-00/64311 discloses composites wherein water-absorbing polymers have been polymerized onto a support material. The composites are used to regulate moisture in seat cushions.
  • JP-A-05-105705 relates to non-flowable dry agent, consisting of a carrier material and hygroscopic salts, wherein the hygroscopic salts are fixed by means of water-absorbing polymers on the support material.
  • Object of the present invention was to provide moisture-regulating composites that can absorb reversibly large amounts of water vapor. Furthermore, the object was to find water vapor-absorbing composites with high mechanical stability.
  • the object of the present invention has been achieved by moisture-regulating composites comprising
  • ratio of hygroscopic substance b) to polymer c) is between 0.01 and 1.
  • the ratio of hygroscopic substance b) to polymer c) is preferably less than 0.8, preferably less than 0.6, more preferably less than 0.5, most preferably less than 0.4, and at least 0.05, preferably at least 0.1, more preferably at least 0.15.
  • the support materials a) are not subject to any restriction.
  • Preferred support materials are fabrics and / or nonwovens, as described in WO-A-01/56625 on page 16, line 40, to page 20, line 27 described.
  • Suitable carrier materials a) are, for example, woven or nonwoven fabrics made of synthetic polymeric fibers.
  • the fibers may be of any spinnable polymeric material, for example, polyolefins such as polyethylene or polypropylene, polyesters such as polyethylene terephthalate, polyamides such as Nylon® 6 or Nylon® 6,6, polyacrylates, modified celluloses such as cellulose acetate.
  • polyolefins such as polyethylene or polypropylene
  • polyesters such as polyethylene terephthalate
  • polyamides such as Nylon® 6 or Nylon® 6,6, polyacrylates
  • modified celluloses such as cellulose acetate.
  • mixtures of the above-mentioned polymeric materials can be used.
  • Fabrics are products of crossed threads, preferably crossed threads at right angles.
  • Nonwovens are nonwoven products made of fibers, where the cohesion is generally given by the inherent adhesion of the fibers.
  • Preferably nonwovens are mechanically consolidated, for example by needling, meshing or vortexing by means of sharp water or air jets.
  • Nonwovens can also be bonded adhesively or cohesively.
  • Adhesively bonded nonwovens are obtainable, for example, by bonding the fibers with liquid binding agents or by melting binder fibers which have been added to the nonwoven during manufacture.
  • Cohesively consolidated nonwovens are obtainable, for example, by dissolving the fibers with suitable chemicals and applying pressure.
  • the support materials advantageously have a weight per unit area of from 20 to 200 g / m 2 , preferably from 30 to 150 g / m 2 , particularly preferably from 35 to 125 g / m 2 .
  • the density of the support materials is usually 0.005 to 0.2 g / cm 3 , preferably from 0.008 to 0.16 g / cm 3 , particularly preferably from 0.01 to 0.14 g / cm 3 .
  • Hygroscopic substances b) are substances capable of absorbing water vapor, that is, water vapor from the air condenses on the hygroscopic substance, whereby the water content of the hygroscopic substance b) increases.
  • Hygroscopic substances b) are, for example, inorganic salts, such as sodium chloride, lead nitrate, zinc sulfate, sodium perchlorate, chromium oxide or lithium chloride, or at least partially crystalline organic compounds, such as water-soluble polyacrylic acids.
  • Hygroscopic inorganic salts are preferred hygroscopic substances b). Most preferred is sodium chloride.
  • Particularly advantageous hygroscopic substances b) are compounds in which above a saturated aqueous solution at 2O 0 C in equilibrium a relative humidity of less than 95%, preferably less than 90%, preferably less than 85%, particularly preferably less than 80% and at least 40%, preferably at least 45%, preferably at least 50%, more preferably at least 55%, most preferably at least 60%.
  • the relative humidity is the quotient of water vapor partial pressure and water vapor pressure multiplied by 100%.
  • the hygroscopic substance b) is distributed in the polymerized-on water-absorbing polymer.
  • relative humidity of more than 90% is perceived as unpleasant, since perspiration is promoted at high air humidity.
  • relative humidities below 40% are also not advantageous since such low relative humidities do not further increase seating comfort and only make it more difficult to desorb already absorbed moisture during periods of non-use.
  • the moisture-regulating composites of the invention can be obtained by polymerization of a monomer solution containing
  • the ratio of hygroscopic substance ii) to monomer i) is preferably less than 0.8, preferably less than 0.6, more preferably less than 0.5, even more preferably less than 0.4, and at least 0.05, preferably at least 0.1, more preferably at least 0.15.
  • Suitable monomers i) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic acid esters. Preference is given to monomers containing acidic groups i). Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
  • Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
  • Tocopherol is understood as meaning compounds of the following formula
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen or methyl
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
  • R 4 Preferred radicals for R 4 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids.
  • the carboxylic acids can be mono-, di- or tricarboxylic acids.
  • R 4 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
  • the monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, especially preferably around 50 ppm by weight, hydroquinone halide, in each case based on acrylic acid, wherein acrylic acid salts are mathematically taken into account as acrylic acid.
  • acrylic acid salts are mathematically taken into account as acrylic acid.
  • an acrylic acid having a corresponding content of hydroquinone half-ether can be used to prepare the monomer solution.
  • hygroscopic substances ii) which can be used in the process according to the invention have already been described above as hygroscopic substances b).
  • the water-absorbing polymers are crosslinked, i. the polymerization is carried out in the presence of compounds having at least two polymerisable groups which can be radically copolymerized into the polymer network.
  • Suitable crosslinkers iii) are, for example, ethylene glycol dimethacrylate, diethylene glycol ideacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A-0 530 438, di- and triacryates, as in EP-A-0 547 847, EP-A-0 559 476, EP-A-0 632 068, WO-A-93/21237, WO-A-03/104299, WO-A-03/104300, WO-A-03/104301 and in DE-A-103 31 450, mixed acrylates, in addition to Acry lat groups contain further ethylenically unsaturated groups, as described in
  • Suitable crosslinkers iii) include in particular N, N'-methylenebisacrylamide and N 1 N'-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids acrylate of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol di acrylate or methacrylate and Trimethyloipropantriacrylat and allyl compounds, such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in EP-AO 343 427.
  • esters of unsaturated mono- or polycarboxylic acids acrylate of polyols such as diacrylate or triacrylate, for example butanediol or ethylene glyco
  • crosslinkers iii) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol di- and glycerol triallyl ether, polyhalide ethers based on sorbitol, and ethoxylated variants thereof.
  • Useful in the process according to the invention are di (meth) acrylates of polyethylene glycols, wherein the polyethylene glycol used has a molecular weight between 300 and 1000.
  • crosslinkers iii) are di- and triacrylates of 3 to 20 times ethoxylated glycerol, 3 to 20 times ethoxylated trimethylolpropane, 3 to 20 times ethoxylated trimethylolethane, in particular di- and triacrylates of 2 to 6-fold ethoxylated glycerol or trimethylolpropane, the 3-fold propoxylated glycerol or trimethylolpropane, and the 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-times ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, Trimethylolethane or trimethylolpropane.
  • Very particularly preferred crosslinkers iii) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in WO-A-03/104301. Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol. Very particular preference is given to diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol. Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerin.
  • acrylamide, methacrylamide, crotonamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate are monomers which can be copolymerized with the monomers i).
  • water-soluble polymers v) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
  • Hygroscopic polymers such as soluble polyacrylic acids, can be used both as a hygroscopic substance ii) and as a water-soluble polymer v).
  • graft polymerization catalysts for example iron salts
  • the polymers will serve as the grafting base for the polymerization and the polymerizing monomers will be grafted onto the polymers. If the use of graft polymerization catalysts is dispensed with, the polymers will survive the polymerization largely unchanged and act as a hygroscopic substance.
  • the acid groups of the preferred monomers i) are usually partially neutralized, preferably from 25 to 95 mol%, preferably from 40 to 90 mol%, particularly preferably from 50 to 80 mol%, very particularly preferably from 60 to 80 mol% ,
  • the usual neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof.
  • alkali metal salts and ammonium salts can be used.
  • Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
  • the neutralization is achieved by mixing the neutralizing agent as an aqueous solution, as a melt, or preferably as a solid.
  • the neutralizing agent for example, sodium hydroxide with a water content well below 50 wt.% May be present as a waxy mass with a melting point above 23 ° C.
  • a dosage as general cargo or melt at elevated temperature is possible.
  • the aqueous monomer solution is applied to the carrier material, preferably sprayed on.
  • the suitable support materials have already been described above as support material a).
  • the monomer solution is polymerized on the support material and the composite is dried.
  • the polymerization is preferably induced by UV radiation and / or thermally.
  • the composites according to the invention are outstandingly suitable for moisture regulation, in particular in mattresses and seat cushions, for example in car seats.
  • Seat cushions or mattresses containing the composites of the present invention increase sitting comfort by controlling the relative humidity to a comfortable level and preventing excessive perspiration.
  • the composites according to the invention can optimally release the absorbed moisture in phases of non-use and regenerate rapidly. Because of this balanced property profile, the composites according to the invention enable hitherto unattainable sitting or lying comfort.
  • the measurements are carried out at an ambient temperature of 23 + 2 0 C.
  • the composites are stored for 30 minutes at a relative humidity of 50% in the climate chamber for equilibrium. Subsequently, the relative Humidity increased to 90% for 60 minutes (absorption phase). Then the relative humidity is lowered again to 50% for 30 minutes (desorption phase).
  • the weight change by absorption / desorption is measured continuously and is the weight gain, based on g applied substance (water-absorbing polymer and / or salt).
  • the reference point for weight gain is the weight after equilibration after 30 minutes.
  • a monomer solution was sprayed and cured by UV radiation for 2 minutes.
  • the terminal was dried for 5 minutes at 90 ° C. in a countercurrent dryer.
  • the monomer solution contained 33.6% by weight of sodium acrylate, 8.5% by weight of acrylic acid, 1.51% by weight of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400), 0.22% by weight of 2- Hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone and water.
  • the amount of monomer solution was chosen so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer was 160 g / m 2 .
  • the monomer solution contained 22.8% by weight of sodium acrylate, 16.9% by weight of acrylic acid, 1.51% by weight of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400), 0.22% by weight of 2- Hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone and water.
  • the amount of monomer solution was chosen so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer was 160 g / m 2 .
  • the monomer solution contained 36.2% by weight of sodium acrylate, 2.0% by weight of acrylic acid, 1.30% by weight of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400), 0.19% by weight of 2- Hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone and water.
  • the amount of monomer solution was chosen so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer was 160 g / m 2 .
  • Example 2 The procedure was as in Example 1. 17 g / m 2 sodium chloride was sprayed as a 25gew .-% aqueous solution of the composition after the polymerization and dried.
  • the composite was not mechanically stable.
  • the sprayed sodium chloride dissolved easily.
  • the monomer solution contained 23.7 wt .-% sodium acrylate, 6.0 wt .-% acrylic acid, 1, 06 wt .-% polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400) , 0.15 wt .-% of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] - 2-methyl-1-propanone, 7.4 wt .-% sodium chloride and water (prepared from a monomer solution according to Example 1 and 42% by weight, based on the monomer solution according to Example 1, of a 25% strength by weight aqueous sodium chloride solution).
  • the amount of monomer solution was selected so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer / sodium chloride was 160 g / m 2 .
  • Example 5 The procedure was as in Example 5. In the monomer solution, polyethylene glycol diacrylate was replaced by 15-fold ethoxylated trimethylolpropane triacrylate.
  • the amount of monomer solution was selected so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer / sodium chloride was 160 g / m 2 .
  • the monomer solution contained 27.8 wt .-% sodium acrylate, 1, 5 wt .-% acrylic acid, 1, 00 wt .-% polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400) , 0.15 wt .-% of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] - 2-methyl-1-propanone, 5.8 wt .-% sodium chloride and water (prepared from a monomer solution according to Example 3 and 30% by weight, based on the monomer solution according to Example 3, of a 25% strength by weight aqueous sodium chloride solution).
  • the amount of monomer solution was selected so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer / sodium chloride was 160 g / m 2 .

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Abstract

The invention relates to humidity-regulating composite materials comprising a flat carrier material, a water-soluble hygroscopic substance, and a water-absorbent polymer which is polymerised on the carrier material in the presence of the hygroscopic substance. The invention also relates to a method for producing said materials, and to the use of the same for humidity regulation.

Description

Feuchtigkeitsregulierende Verbundstoffe Moisture-regulating composites
Beschreibungdescription
Die vorliegende Erfindung betrifft feuchtigkeitsreglierende Verbundstoffe, Verfahren zu ihrer Herstellung sowie deren Verwendung zur Feuchtigkeitsregulierung.The present invention relates to moisture-controlling composites, to processes for their preparation and to their use for moisture regulation.
Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen.Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular combination specified, but also in other combinations, without departing from the scope of the invention.
Wasserabsorbierende Polymere sind insbesondere Polymere aus (co)polymerisierten hydrophilen Monomeren, Pfropf(co)polymere von einem oder mehreren hydrophilen Monomeren auf einer geeigneten Pfropfgrundlage, vernetzte Cellulose- oder Stärke- ether, vernetzte Carboxymethylcellulose, teilweise vernetztes Polyalkylenoxid oder in wässrigen Flüssigkeiten quellbare Naturprodukte, wie beispielsweise Guarderivate. Solche Polymere werden als wässrige Lösungen absorbierende Produkte zur Herstellung von Windeln, Tampons, Damenbinden und anderen Hygieneartikeln, aber auch als wasserzurückhaltende Mittel im landwirtschaftlichen Gartenbau verwendet.Water-absorbing polymers are, in particular, polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives. Such polymers are used as aqueous solution-absorbing products for making diapers, tampons, sanitary napkins and other sanitary articles, but also as water-retaining agents in agricultural horticulture.
Die Herstellung wasserabsorbierender Polymere wird in der Monographie "Modem Superabsorbent Polymer Technology", F.L. Buchholz und A.T. Graham, Wiley-VCH, 1998, Seiten 69 bis 117, beschrieben.The preparation of water-absorbing polymers is described in the monograph "Modem Superabsorbent Polymer Technology", F.L. Buchholz and A.T. Graham, Wiley-VCH, 1998, pages 69-117.
WO-A-01/56625, EP-A-1 178 149 und US-5,962,068 beschreiben Verfahren zur Herstellung wasserabsorbierender Verbundstoffe, bei denen wasserabsorbierende PoIy- mere auf ein Trägermaterial aufpolymerisiert werden.WO-A-01/56625, EP-A-1 178 149 and US Pat. No. 5,962,068 describe processes for producing water-absorbing composites in which water-absorbing polymers are copolymerized onto a support material.
Die WO-A-00/64311 offenbart Verbundstoffe bei denen wasserabsorbierende Polymere auf ein Trägermaterial polymerisiert wurden. Die Verbundstoffe werden zur Feuchtigkeitsregulierung in Sitzpolstern verwendet.WO-A-00/64311 discloses composites wherein water-absorbing polymers have been polymerized onto a support material. The composites are used to regulate moisture in seat cushions.
JP-A- 05-105705 betrifft nichtzerfließende Trocken mittel, bestehend aus einem Trägermaterial und hygroskopischen Salzen, wobei die hygroskopischen Salze mittels wasserabsorbierender Polymere auf dem Trägermaterial fixiert werden.JP-A-05-105705 relates to non-flowable dry agent, consisting of a carrier material and hygroscopic salts, wherein the hygroscopic salts are fixed by means of water-absorbing polymers on the support material.
Aufgabe der vorliegenden Erfindung war die Bereitstellung feuchtigkeitsregulierender Verbundstoffe, die reversibel große Mengen Wasserdampf aufnehmen können. Weiterhin bestand die Aufgabe, wasserdampfabsorbierende Verbundstoffe mit hoher mechanischer Stabilität zu finden.Object of the present invention was to provide moisture-regulating composites that can absorb reversibly large amounts of water vapor. Furthermore, the object was to find water vapor-absorbing composites with high mechanical stability.
Gelöst wurde die Aufgabe der vorliegenden Erfindung durch feuchtigkeitsregulierende Verbundstoffe, umfassendThe object of the present invention has been achieved by moisture-regulating composites comprising
a) mindestens ein flächiges Trägermaterial, b) mindestens eine wasserlösliche hygroskopische Substanz und c) mindestens ein in Gegenwart der Substanz b) auf das Trägermaterial a) aufpo- lymerisiertes wasserabsorbierendes Polymer,a) at least one planar carrier material, b) at least one water-soluble hygroscopic substance and c) at least one water-absorbing polymer which is polymerized in the presence of the substance b) onto the carrier material a),
wobei das Verhältnis von hygroskopischer Substanz b) zu Polymer c) zwischen 0,01 und 1 beträgt.wherein the ratio of hygroscopic substance b) to polymer c) is between 0.01 and 1.
Das Verhältnis von hygroskopischer Substanz b) zu Polymer c) beträgt vorzugsweise weniger als 0,8, bevorzugt weniger als 0,6, besonders bevorzugt weniger als 0,5, ganz besonders bevorzugt weniger als 0,4, und mindestens 0,05, bevorzugt mindestens 0,1, besonders bevorzugt mindestens 0,15.The ratio of hygroscopic substance b) to polymer c) is preferably less than 0.8, preferably less than 0.6, more preferably less than 0.5, most preferably less than 0.4, and at least 0.05, preferably at least 0.1, more preferably at least 0.15.
Die Trägermaterialien a) unterliegen keiner Beschränkung. Bevorzugte Trägermaterialien sind Gewebe und/oder Vliese, wie in der WO-A-01/56625 auf Seite 16, Zeile 40, bis Seite 20, Zeile 27, beschrieben werden.The support materials a) are not subject to any restriction. Preferred support materials are fabrics and / or nonwovens, as described in WO-A-01/56625 on page 16, line 40, to page 20, line 27 described.
Geeignete Trägermaterialien a) sind beispielsweise Gewebe oder Vliese aus syntheti- sehen polymeren Fasern. Die Fasern können aus jedem spinnbaren polymeren Material sein, beispielsweise Polyolefine, wie Polyethylen oder Polypropylen, Polyester, wie Polyethylenterephthalat, Polyamide, wie Nylon® 6 oder Nylon® 6,6, Polyacrylate, modifizierte Zellulosen, wie Zelluloseacetat. Weiterhin können auch Gemische obengenannter polymeren Materialien eingesetzt werden.Suitable carrier materials a) are, for example, woven or nonwoven fabrics made of synthetic polymeric fibers. The fibers may be of any spinnable polymeric material, for example, polyolefins such as polyethylene or polypropylene, polyesters such as polyethylene terephthalate, polyamides such as Nylon® 6 or Nylon® 6,6, polyacrylates, modified celluloses such as cellulose acetate. Furthermore, mixtures of the above-mentioned polymeric materials can be used.
Gewebe sind Erzeugnisse aus gekreuzten Fäden, vorzugsweise rechtwinklig gekreuzten Fäden.Fabrics are products of crossed threads, preferably crossed threads at right angles.
Vliese sind nicht gewebte Erzeugnisse aus Fasern, bei denen der Zusammenhalt im allgemeinen durch die den Fasern eigene Haftung gegeben ist. Vorzugsweise werden Vliese mechanisch verfestigt, beispielsweise durch Vernadeln, Vermaschen oder Ver- wirbeln mittels scharfer Wasser- oder Luftstrahlen. Vliese können auch adhäsiv oder kohäsiv verfestigt werden. Adhäsiv verfestigte Vliese sind beispielsweise erhältlich durch Verkleben der Fasern mit flüssigen Bindemiteln oder durch Schmelzen von Bin- defasern, die dem Vlies bei der Herstellung zugesetzt wurden. Kohäsiv verfestigte Vliese sind beispielsweise durch Anlösen der Fasern mit geeigneten Chemikalien und Anwendung von Druck erhältlich. Die Trägermaterialien weisen zweckmäßigerweise ein Flächengewicht von 20 bis 200 g/m2, vorzugsweise von 30 bis 150 g/m2, besonders bevorzugt von 35 bis 125 g/m2, auf.Nonwovens are nonwoven products made of fibers, where the cohesion is generally given by the inherent adhesion of the fibers. Preferably nonwovens are mechanically consolidated, for example by needling, meshing or vortexing by means of sharp water or air jets. Nonwovens can also be bonded adhesively or cohesively. Adhesively bonded nonwovens are obtainable, for example, by bonding the fibers with liquid binding agents or by melting binder fibers which have been added to the nonwoven during manufacture. Cohesively consolidated nonwovens are obtainable, for example, by dissolving the fibers with suitable chemicals and applying pressure. The support materials advantageously have a weight per unit area of from 20 to 200 g / m 2 , preferably from 30 to 150 g / m 2 , particularly preferably from 35 to 125 g / m 2 .
Die Dichte der Trägermaterialien beträgt üblicherweise 0,005 bis 0,2 g/cm3, vorzugsweise von 0,008 bis 0,16 g/cm3, besonders bevorzugt von 0,01 bis 0,14 g/cm3.The density of the support materials is usually 0.005 to 0.2 g / cm 3 , preferably from 0.008 to 0.16 g / cm 3 , particularly preferably from 0.01 to 0.14 g / cm 3 .
Hygroskopische Substanzen b) sind Stoffe, die in der Lage sind Wasserdampf zu ab- sorbieren, d.h., Wasserdampf aus der Luft kondensiert auf der hygroskopischen Substanz, wobei der Wassergehalt der hygroskopischen Substanz b) steigt. Hygroskopische Substanzen b) sind beispielsweise anorganische Salze, wie Natriumchlorid, Bleinitrat, Zinksulfat, Natriumperchlorat, Chromoxid oder Lithiumchlorid, oder zumindest teilkristalline organische Verbindungen, wie wasserlösliche Polyacrylsäuren. Hygro- skopische anorganische Salze sind bevorzugte hygroskopische Substanzen b). Ganz besonders bevorzugt ist Natriumchlorid.Hygroscopic substances b) are substances capable of absorbing water vapor, that is, water vapor from the air condenses on the hygroscopic substance, whereby the water content of the hygroscopic substance b) increases. Hygroscopic substances b) are, for example, inorganic salts, such as sodium chloride, lead nitrate, zinc sulfate, sodium perchlorate, chromium oxide or lithium chloride, or at least partially crystalline organic compounds, such as water-soluble polyacrylic acids. Hygroscopic inorganic salts are preferred hygroscopic substances b). Most preferred is sodium chloride.
Besonders vorteilhafte hygroskopische Substanzen b) sind Verbindungen, bei denen sich über einer gesättigten wässrigen Lösung bei 2O0C im Gleichgewicht eine relative Feuchte von weniger als 95%, vorzugsweise weniger als 90%, bevorzugt weniger als 85%, besonders bevorzugt weniger als 80%, und von mindestens 40%, vorzugsweise mindesten 45%, bevorzugt mindestens 50%, besonders bevorzugt mindestens 55%, ganz besonders bevorzugt mindesten 60%, einstellt.Particularly advantageous hygroscopic substances b) are compounds in which above a saturated aqueous solution at 2O 0 C in equilibrium a relative humidity of less than 95%, preferably less than 90%, preferably less than 85%, particularly preferably less than 80% and at least 40%, preferably at least 45%, preferably at least 50%, more preferably at least 55%, most preferably at least 60%.
Die relative Feuchte ist der Quotient aus Wasserdampfpartialdruck und Wasserdampfdruck multipliziert mit 100%.The relative humidity is the quotient of water vapor partial pressure and water vapor pressure multiplied by 100%.
Vorzugsweise liegt die hygroskopische Substanz b) im aufpolymerisiertem wasserabsorbierenden Polymer verteilt vor.Preferably, the hygroscopic substance b) is distributed in the polymerized-on water-absorbing polymer.
Bei der Verwendung der erfindungsgemäßen feuchtigkeitsregulierenden Verbundstoffe, beispielsweise in Sitzpolstern, werden relative Feuchten von über 90% als unangenehm empfunden, da bei hoher Luftfeuchtigkeit die Schweißbildung begünstigt wird. Relative Feuchten unter 40% sind aber auch nicht vorteilhaft, da derart niedrige relative Feuchten den Sitzkomfort nicht weiter erhöhen und nur die Desorption bereits aufgenommener Feuchtigkeit in Phasen der Nichtbenutzung erschweren.When using the moisture-regulating composites according to the invention, for example in seat cushions, relative humidity of more than 90% is perceived as unpleasant, since perspiration is promoted at high air humidity. However, relative humidities below 40% are also not advantageous since such low relative humidities do not further increase seating comfort and only make it more difficult to desorb already absorbed moisture during periods of non-use.
Die erfindungsgemäßen feuchtigkeitsregulierenden Verbundstoffe können durch Polymerisation einer Monomerlösung, enthaltendThe moisture-regulating composites of the invention can be obtained by polymerization of a monomer solution containing
i) mindestens ein ethylenisch ungesättigtes Monomer, ii) mindestens eine hygroskopische Substanz, iii) mindestens einen Vernetzer, iv) gegebenenfalls ein oder mehrere mit den unter i) genannten Monomeren copo- lymerisierbare ethylenisch und/oder allylisch ungesättigte Monomere und v) gegebenenfalls ein oder mehrere wasserlösliche Polymere,i) at least one ethylenically unsaturated monomer, ii) at least one hygroscopic substance, iii) at least one crosslinker, iv) optionally one or more ethylenically and / or allylically unsaturated monomers which can be copolymerized with the monomers mentioned under i) and v) optionally one or more water-soluble polymers,
welche auf ein Trägermaterial aufgebracht und polymerisiert wird, erhalten werden, wobei das Verhältnis von hygroskopischer Substanz ii) zu Monomer i) zwischen 0,01 und 1 beträgt.which is applied to a support material and polymerized, can be obtained, wherein the ratio of hygroscopic substance ii) to monomer i) is between 0.01 and 1.
Das Verhältnis von hygroskopischer Substanz ii) zu Monomer i) beträgt vorzugsweise weniger als 0,8, bevorzugt weniger als 0,6, besonders bevorzugt weniger als 0,5, ganz besonders bevorzugt weinger als 0,4, und mindestens 0,05, bevorzugt mindestens 0,1, besonders bevorzugt mindestens 0,15.The ratio of hygroscopic substance ii) to monomer i) is preferably less than 0.8, preferably less than 0.6, more preferably less than 0.5, even more preferably less than 0.4, and at least 0.05, preferably at least 0.1, more preferably at least 0.15.
Geeignete Monomere i) sind beispielsweise ethylenisch ungesättigte Carbonsäuren, wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure und Itaconsäure, oder deren Derivate, wie Acrylamid, Methacrylamid, Acrylsäureester und Methacrylsäureester. Bevorzugt sind saure Gruppen enthaltende Monomere i). Besonders bevorzugte Monomere sind Acrylsäure und Methacrylsäure. Ganz besonders bevorzugt ist Acrylsäu- re.Suitable monomers i) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic acid esters. Preference is given to monomers containing acidic groups i). Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
Die Monomere i), insbesondere Acrylsäure, enthalten vorzugsweise bis zu 0,025 Gew.- % eines Hydrochinonhalbethers. Bevorzugte Hydrochinonhalbether sind Hydrochinon- monomethylether (MEHQ) und/oder Tocopherole.The monomers i), in particular acrylic acid, preferably contain up to 0.025% by weight of a hydroquinone half ether. Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
Unter Tocopherol werden Verbindungen der folgenden Formel verstandenTocopherol is understood as meaning compounds of the following formula
wobei R1 Wasserstoff oder Methyl, R2 Wasserstoff oder Methyl, R3 Wasserstoff oder Methyl und R4 Wasserstoff oder ein Säurerest mit 1 bis 20 Kohlenstoffatomen bedeutet.wherein R 1 is hydrogen or methyl, R 2 is hydrogen or methyl, R 3 is hydrogen or methyl and R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
Bevorzugte Reste für R4 sind Acetyl, Ascorbyl, Succinyl, Nicotinyl und andere physio- logisch verträgliche Carbonsäuren. Die Carbonsäuren können Mono-, Di- oder Tricar- bonsäuren sein. Bevorzugt ist alpha-Tocopherol mit R1 = R2 = R3 = Methyl, insbesondere racemisches alpha-TocopheroI. R4 ist besonders bevorzugt Wasserstoff oder Acetyl. Insbesondere bevorzugt ist RRR-alpha-Tocopherol.Preferred radicals for R 4 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids. The carboxylic acids can be mono-, di- or tricarboxylic acids. Preference is given to alpha-tocopherol with R 1 = R 2 = R 3 = methyl, in particular racemic alpha-tocopherol. R 4 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
Die Monomerlösung enthält bevorzugt höchstens 130 Gew.-ppm, besonders bevorzugt höchstens 70 Gew.-ppm, bevorzugt mindestens 10 Gew.-ppm, besonders bevorzugt mindestens 30 Gew.-ppm, insbesondere bevorzugt um 50 Gew.-ppm, Hydrochinonhal- bether, jeweils bezogen auf Acrylsäure, wobei Acrylsäuresalze rechnerisch als Acryl- säure mit berücksichtigt werden. Beispielsweise kann zur Herstellung der Monomerlö- sung eine Acrylsäure mit einem entsprechenen Gehalt an Hydrochinonhalbether verwendet werden.The monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, especially preferably around 50 ppm by weight, hydroquinone halide, in each case based on acrylic acid, wherein acrylic acid salts are mathematically taken into account as acrylic acid. For example, an acrylic acid having a corresponding content of hydroquinone half-ether can be used to prepare the monomer solution.
Die im erfindungsgemäßen Verfahren einsetzbaren hygroskopischen Substanzen ii) wurden bereits oben als hygroskopische Substanzen b) beschrieben.The hygroscopic substances ii) which can be used in the process according to the invention have already been described above as hygroscopic substances b).
Die wasserabsorbierenden Polymere sind vernetzt, d.h. die Polymerisation wird in Gegenwart von Verbindungen mit mindestens zwei polymerisierbaren Gruppen, die in das Polymernetzwerk radikalisch einpolymerisiert werden können, durchgeführt. Geeignete Vernetzer iii) sind beispielsweise Ethylenglykoldimethacrylat, Diethylenglykoidiacrylat, Allylmethacrylat, Trimethyloipropantriacrylat, Triallylamin, Tetraallyloxyethan, wie in EP-A-O 530 438 beschrieben, Di- und Triacryiate, wie in EP-A-O 547 847, EP-A-O 559 476, EP-A-O 632 068, WO-A-93/21237, WO-A-03/104299, WO-A-03/104300, WO-A- 03/104301 und in DE-A-103 31 450 beschrieben, gemischte Acrylate, die neben Acry- latgruppen weitere ethyienisch ungesättigte Gruppen enthalten, wie in DE-A-103 314 56 und der älteren deutschen Anmeldung mit dem Aktenzeichen 10355401.7 beschrieben, oder Vernetzermischungen, wie beispielsweise in DE-A-19543 368, DE-A-19646 484, WO-A-90/15830 und WO-A-02/32962 beschrieben.The water-absorbing polymers are crosslinked, i. the polymerization is carried out in the presence of compounds having at least two polymerisable groups which can be radically copolymerized into the polymer network. Suitable crosslinkers iii) are, for example, ethylene glycol dimethacrylate, diethylene glycol ideacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A-0 530 438, di- and triacryates, as in EP-A-0 547 847, EP-A-0 559 476, EP-A-0 632 068, WO-A-93/21237, WO-A-03/104299, WO-A-03/104300, WO-A-03/104301 and in DE-A-103 31 450, mixed acrylates, in addition to Acry lat groups contain further ethylenically unsaturated groups, as described in DE-A-103 314 56 and the earlier German application with the file reference 10355401.7, or crosslinker mixtures, as described, for example, in DE-A-19543 368, DE-A-19646 484, WO-A A-90/15830 and WO-A-02/32962.
Geeignete Vernetzer iii) sind insbesondere N.N'-Methylenbisacrylamid und N1N'- Methylenbismethacrylamid, Ester ungesättigter Mono- oder Polycarbonsäuren von Polyolen, wie Diacrylat oder Triacrylat, beispielsweise Butandiol- oder Ethylenglykoldi- acrylat bzw. -methacrylat sowie Trimethyloipropantriacrylat und Allylverbindungen, wie Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraallyloxyethan, Triallylamin, Tetraallylethylendiamin, Allylester der Phosphorsäure sowie Vi- nylphosphonsäurederivate, wie sie beispielsweise in EP-A-O 343 427 beschrieben sind. Weiterhin geeignete Vernetzer iii) sind Pentaerythritoldi-, Pentaerythritoltri- und Pentaerythritoltetraallylether, Polyethylenglykoldiallylether, Ethylenglykoldiallyiether, Glyzerindi- und Glyzerintriallylether, Polyailylether auf Basis Sorbitol, sowie ethoxylier- te Varianten davon. Im erfindungsgemäßen Verfahren einsetzbar sind Di(meth)acrylate von Polyethylenglykolen, wobei das eingesetzte Polyethylenglykol ein Molekulargewicht zwischen 300 und 1000 aufweist. Besonders vorteilhafte Vernetzer iii) sind jedoch Di- und Triacrylate des 3- bis 20-fach ethoxylierten Glyzerins, des 3- bis 20-fach ethoxylierten Trimethylolpropans, des 3- bis 20-fach ethoxylierten Trimethylolethans, inbesondere Di- und Triacrylate des 2- bis 6- fach ethoxylierten Glyzerins oder Trimethylolpropans, des 3-fach propoxylierten Glyze- rins oder Trimethylolpropans, sowie des 3-fach gemischt ethoxylierten oder propoxylierten Glyzerins oder Trimethylolpropans, des 15-fach ethoxylierten Glyzerins oder Trimethylolpropans, sowie des mindestens 40-fach ethoxylierten Glyzerins, Trimethylolethans oder Trimethylolpropans.Suitable crosslinkers iii) include in particular N, N'-methylenebisacrylamide and N 1 N'-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids acrylate of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol di acrylate or methacrylate and Trimethyloipropantriacrylat and allyl compounds, such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in EP-AO 343 427. Further suitable crosslinkers iii) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol di- and glycerol triallyl ether, polyhalide ethers based on sorbitol, and ethoxylated variants thereof. Useful in the process according to the invention are di (meth) acrylates of polyethylene glycols, wherein the polyethylene glycol used has a molecular weight between 300 and 1000. However, particularly advantageous crosslinkers iii) are di- and triacrylates of 3 to 20 times ethoxylated glycerol, 3 to 20 times ethoxylated trimethylolpropane, 3 to 20 times ethoxylated trimethylolethane, in particular di- and triacrylates of 2 to 6-fold ethoxylated glycerol or trimethylolpropane, the 3-fold propoxylated glycerol or trimethylolpropane, and the 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-times ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, Trimethylolethane or trimethylolpropane.
Ganz besonders bevorzugte Vernetzer iii) sind die mit Acrylsäure oder Methacrylsäure zu Di- oder Triacrylaten veresterten mehrfach ethoxylierten und/oder propoxylierten Glyzerine wie sie beispielsweise in WO-A-03/104301 beschrieben sind. Besonders vorteilhaft sind Di- und/oder Triacrylate des 3- bis 10-fach ethoxylierten Glyzerins. Ganz besonders bevorzugt sind Di- oder Triacrylate des 1- bis 5- fach ethoxylierten und/oder propoxylierten Glyzerins. Am meisten bevorzugt sind die Triacrylate des 3- bis 5-fach ethoxylierten und/oder propoxylierten Glyzerins. Diese zeichnen sich durch besonders niedrige Restgehalte (typischerweise unter 10 Gew.-ppm) im wasserabor- bierenden Polymer aus und die wässrigen Extrakte der damit hergestellten wasserabsorbierenden Polymere weisen eine fast unveränderte Oberflächenspannung (typi- scherweise mindestens 0,068 N/m) im Vergleich zu Wasser gleicher Temperatur auf.Very particularly preferred crosslinkers iii) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in WO-A-03/104301. Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol. Very particular preference is given to diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol. Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerin. These are distinguished by particularly low residual contents (typically below 10 ppm by weight) in the water-laborizing polymer and the aqueous extracts of the water-absorbing polymers produced therewith have an almost unchanged surface tension (typically at least 0.068 N / m) compared to water same temperature.
Mit den Monomeren i) copolymerisierbare ethylenisch ungesättigte Monomere iv) sind beispielsweise Acrylamid, Methacrylamid, Crotonsäureamid, Dimethylaminoethyl- methacrylat, Dimethylaminoethylacrylat, Dimethylaminopropylacrylat, Diethylaminopro- pylacrylat, Dimethylaminobutylacrylat, Dimethylaminoethylmethacrylat, Diethylami- noethylmethacrylat, Dimethylaminoneopentylacrylat und Dimethylaminoneopentyl- methacrylat.For example, acrylamide, methacrylamide, crotonamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate are monomers which can be copolymerized with the monomers i).
Als wasserlösliche Polymere v) können Polyvinylalkohol, Polyvinylpyrrolidon, Stärke, Stärkederivate, Polyglykole oder Polyacrylsäuren, vorzugsweise Polyvinylalkohol und Stärke, eingesetzt werden.As water-soluble polymers v) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
Hygroskopische Polymere, wie lösliche Polyacrylsäuren, können sowohl als hygroskopische Substanz ii) als auch als wasserlösliches Polymer v) eingesetzt werden.Hygroscopic polymers, such as soluble polyacrylic acids, can be used both as a hygroscopic substance ii) and as a water-soluble polymer v).
Werden der Monomerlösung übliche Pfropfpolymerisationskatalysatoren, beispielsweise Eisensalze, zugesetzt, so werden die Polymere als Pfropfgrundlage für die Polymerisation dienen und die polymerisierenden Monomere auf die Polymeren aufgepfropft werden. Wird auf den Einsatz von Pfropfpolymerisationskatalysatoren verzichtet, so werden die Polymeren die Polymerisation weitgehend unverändert überstehen und als hygroskopische Substanz wirken. Die Säuregruppen der bevorzugten Monomere i) sind üblicherweise teilweise neutralisiert, vorzugsweise zu 25 bis 95 mol-%, bevorzugt zu 40 bis 90 mol-%, besonders bevorzugt zu 50 bis 80 mol-%, ganz besonders bevorzugt zu 60 bis 80 mol-%, wobei die üblichen Neutralisationsmittel verwendet werden können, vorzugsweise Alkalimetall- hydroxide, Alkalimetalloxide, Alkalimetallcarbonate oder Alkalimetallhydrogencarbonate sowie deren Mischungen. Statt Alkalimetallsalzen können auch Ammoniumsalze verwendet werden. Natrium und Kalium sind als Alkalimetalle besonders bevorzugt, ganz besonders bevorzugt sind jedoch Natriumhydroxid, Natriumcarbonat oder Natrium- hydrogencarbonat sowie deren Mischungen. Üblicherweise wird die Neutralisation durch Einmischung des Neutralisationsmittels als wässrige Lösung, als Schmelze, oder bevorzugt auch als Feststoff erreicht. Beispielsweise kann Natriumhydroxid mit einem Wasseranteil deutlich unter 50 Gew.% als wachsartige Masse mit einem Schmelzpunkt oberhalb 23°C vorliegen. In diesem Fall ist eine Dosierung als Stückgut oder Schmelze bei erhöhter Temperatur möglich.If customary graft polymerization catalysts, for example iron salts, are added to the monomer solution, the polymers will serve as the grafting base for the polymerization and the polymerizing monomers will be grafted onto the polymers. If the use of graft polymerization catalysts is dispensed with, the polymers will survive the polymerization largely unchanged and act as a hygroscopic substance. The acid groups of the preferred monomers i) are usually partially neutralized, preferably from 25 to 95 mol%, preferably from 40 to 90 mol%, particularly preferably from 50 to 80 mol%, very particularly preferably from 60 to 80 mol% , Where the usual neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used. Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof. Usually, the neutralization is achieved by mixing the neutralizing agent as an aqueous solution, as a melt, or preferably as a solid. For example, sodium hydroxide with a water content well below 50 wt.% May be present as a waxy mass with a melting point above 23 ° C. In this case, a dosage as general cargo or melt at elevated temperature is possible.
Die wässrige Monomerlösung wird auf das Trägermaterial aufgebracht, vorzugsweise aufgesprüht. Die geeigneten Trägermaterialien wurden bereits oben als Trägermaterial a) beschrieben.The aqueous monomer solution is applied to the carrier material, preferably sprayed on. The suitable support materials have already been described above as support material a).
Anschließend wird die Monomerlösung auf dem Trägermaterial polymerisiert und der Verbundstoff getrocknet. Die Polymerisation wird vorzugsweise durch UV-Strahlung und/oder thermisch induziert.Subsequently, the monomer solution is polymerized on the support material and the composite is dried. The polymerization is preferably induced by UV radiation and / or thermally.
Die erfindungsgemäßen Verbundstoffe eignen sich vorzüglich zur Feuchtigkeitsregulie- rung, insbesondere in Matratzen und Sitzpolstern, beispielsweise in Autositzen.The composites according to the invention are outstandingly suitable for moisture regulation, in particular in mattresses and seat cushions, for example in car seats.
Sitzpolster oder Matratzen, enthaltend die erfindungsgemäßen Verbundstoffe, erhöhen den Sitz- bzw. Liegekomfort, indem sie die relative Luftfeuchtigkeit auf ein angenehmes Maß regulieren und übermäßiges Schwitzen verhindern. Gleichzeitig können die erfin- dungsgemäßen Verbundstoffe die aufgenommene Feuchtigkeit in Phasen der Nichtbenutzung optimal wieder abgeben und sich schnell regenerieren. Aufgrund dieses ausgewogenen Eigenschaftsprofils ermöglichen die erfindungsgemäßen Verbundstoffe einen bisher unerreichten Sitz- bzw. Liegekomfort.Seat cushions or mattresses containing the composites of the present invention increase sitting comfort by controlling the relative humidity to a comfortable level and preventing excessive perspiration. At the same time, the composites according to the invention can optimally release the absorbed moisture in phases of non-use and regenerate rapidly. Because of this balanced property profile, the composites according to the invention enable hitherto unattainable sitting or lying comfort.
Methoden:methods:
Bestimmung der FeuchtigkeitsaufnahmeDetermination of moisture absorption
Die Messungen werden bei einer Umgebungstemperatur von 23 + 2 0C durchgeführt.The measurements are carried out at an ambient temperature of 23 + 2 0 C.
Die Verbundstoffe werden 30 Minuten bei einer relative Luftfeuchtigkeit von 50% im Klimaschrank zur Gleichgewichtseinstellung gelagert. Anschließend wird die relative Luftfeuchtigkeit für 60 Minuten auf 90% erhöht (Absorptionsphase). Danach wird die relative Luftfeuchtigkeit wieder für 30 Minuten auf 50% gesenkt (Desorptionsphase).The composites are stored for 30 minutes at a relative humidity of 50% in the climate chamber for equilibrium. Subsequently, the relative Humidity increased to 90% for 60 minutes (absorption phase). Then the relative humidity is lowered again to 50% for 30 minutes (desorption phase).
Die Gewichtsänderung durch Absorption/Desorption wird kontinuierlich gemessen und ist die Gewichtszunahme, bezogen auf g aufgebrachter Substanz (wasserabsorbierendes Polymer und/oder Salz). Bezugspunkt für die Gewichtszunahme ist das Gewicht nach Gleichgewichtseinstellung nach 30 Minuten.The weight change by absorption / desorption is measured continuously and is the weight gain, based on g applied substance (water-absorbing polymer and / or salt). The reference point for weight gain is the weight after equilibration after 30 minutes.
BeispieleExamples
Beispiel 1example 1
Auf ein Polyethylenterephthalt-Vlies mit einem Flächengewicht von 70 g/m2 wurde eine Monomerlösung aufgesprüht und 2 Minuten mittels UV-Strahlung gehärtet. Anschlie- ß>end wurde für 5 Minuten bei 900C in einem Gegenstromtrockner getrocknet.On a polyethylene terephthalate nonwoven having a basis weight of 70 g / m 2 , a monomer solution was sprayed and cured by UV radiation for 2 minutes. The terminal was dried for 5 minutes at 90 ° C. in a countercurrent dryer.
Die Monomerlösung enthielt 33,6 Gew.-% Natriumacrylat, 8,5 Gew.-% Acrylsäure, 1,51 Gew.-% Polyethylenglykoldiacrylat (Diacrylat eines Polyethylenglykols mit einer mittleren Molmasse von 400), 0,22 Gew.-% 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]- 2- methyl-1-propanon und Wasser.The monomer solution contained 33.6% by weight of sodium acrylate, 8.5% by weight of acrylic acid, 1.51% by weight of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400), 0.22% by weight of 2- Hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone and water.
Die Menge an Monomerlösung wurde so gewählt, dass die Beladung des Polyethylen- terephthalat-Vlieses mit aufpolymerisiertem wasserabsorbierendem Polymer 160 g/m2 betrug.The amount of monomer solution was chosen so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer was 160 g / m 2 .
Anschließend wurde die Feuchtigkeitsaufnahme gemessen. Die Messergebnise sind in der Tabelle 1 zusammengefasst.Subsequently, the moisture absorption was measured. The measurement results are summarized in Table 1.
Beispiel 2Example 2
Es wurde verfahren wie unter Beispiel 1.The procedure was as in Example 1.
Die Monomerlösung enthielt 22,8 Gew.-% Natriumacrylat, 16,9 Gew.-% Acrylsäure, 1,51 Gew.-% Polyethylenglykoldiacrylat (Diacrylat eines Polyethylenglykols mit einer mittleren Molmasse von 400), 0,22 Gew.-% 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]- 2- methyl-1-propanon und Wasser.The monomer solution contained 22.8% by weight of sodium acrylate, 16.9% by weight of acrylic acid, 1.51% by weight of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400), 0.22% by weight of 2- Hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone and water.
Die Menge an Monomerlösung wurde so gewählt, dass die Beladung des Polyethylen- terephthalat-Vlieses mit aufpolymerisiertem wasserabsorbierendem Polymer 160 g/m2 betrug.The amount of monomer solution was chosen so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer was 160 g / m 2 .
Die Messergebnise sind in der Tabelle 1 zusammengefasst. Beispiel 3The measurement results are summarized in Table 1. Example 3
Es wurde verfahren wie unter Beispiel 1.The procedure was as in Example 1.
Die Monomerlösung enthielt 36,2 Gew.-% Natriumacrylat, 2,0 Gew.-% Acrylsäure, 1,30 Gew.-% Polyethylenglykoldiacrylat (Diacrylat eines Polyethylenglykols mit einer mittleren Molmasse von 400), 0,19 Gew.-% 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]- 2- methyt-1-propanon und Wasser.The monomer solution contained 36.2% by weight of sodium acrylate, 2.0% by weight of acrylic acid, 1.30% by weight of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400), 0.19% by weight of 2- Hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone and water.
Die Menge an Monomerlösung wurde so gewählt, dass die Beladung des Polyethylen- terephthalat- Vlieses mit aufpolymerisiertem wasserabsorbierendem Polymer 160 g/m2 betrug.The amount of monomer solution was chosen so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer was 160 g / m 2 .
Die Messergebnise sind in der Tabelle 1 zusammengefasst.The measurement results are summarized in Table 1.
Beispiel 4Example 4
Es wurde verfahren wie unter Beispiel 1. Auf den Verbundstoff wurde nach der PoIy- merisation 17 g/m2 Natriumchlorid als 25gew.-%ige wässrige Lösung aufgesprüht und getrocknet.The procedure was as in Example 1. 17 g / m 2 sodium chloride was sprayed as a 25gew .-% aqueous solution of the composition after the polymerization and dried.
Der Verbundstoff war nicht mechanisch stabil. Das aufgesprühte Natriumchlorid löste sich leicht ab.The composite was not mechanically stable. The sprayed sodium chloride dissolved easily.
Beispiel 5Example 5
Es wurde verfahren wie unter Beispiel 1. Die Monomerlösung enthielt 23,7 Gew.-% Natriumacrylat, 6,0 Gew.-% Acrylsäure, 1 ,06 Gew.-% Polyethylenglykoldiacrylat (Diac- rylat eines Polyethylenglykols mit einer mittleren Molmasse von 400), 0,15 Gew.-% 2- Hydroxy-1-[4-(hydroxyethoxy)phenyl]- 2-methyl-1-propanon, 7,4 Gew.-% Natriumchlorid und Wasser (hergestellt aus einer Monomerlösung gemäß Beispiel 1 und 42 Gew.- %, bezogen auf die Monomerlösung gemäß Beispiel 1 , einer 25 gew.-%igen wässrigen Kochsalzlösung).The procedure was as in Example 1. The monomer solution contained 23.7 wt .-% sodium acrylate, 6.0 wt .-% acrylic acid, 1, 06 wt .-% polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400) , 0.15 wt .-% of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] - 2-methyl-1-propanone, 7.4 wt .-% sodium chloride and water (prepared from a monomer solution according to Example 1 and 42% by weight, based on the monomer solution according to Example 1, of a 25% strength by weight aqueous sodium chloride solution).
Die Menge an Monomerlösung wurde so gewählt, dass die Beladung des Polyethylen- terephthalat-Vlieses mit aufpolymerisiertem wasserabsorbierendem Polymer/Natriumchlorid 160 g/m2 betrug.The amount of monomer solution was selected so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer / sodium chloride was 160 g / m 2 .
Die Messergebnise sind in der Tabelle 1 zusammengefasst. Beispiel 6The measurement results are summarized in Table 1. Example 6
Es wurde verfahren wie unter Beispiel 5. In der Monomerlösung wurde Polyethylengly- koldiacrylat durch 15fach ethoxiliertes Trimethylolpropantriacrylat ersetzt.The procedure was as in Example 5. In the monomer solution, polyethylene glycol diacrylate was replaced by 15-fold ethoxylated trimethylolpropane triacrylate.
Die Menge an Monomerlösung wurde so gewählt, dass die Beladung des Polyethylen- terephthalat-Vlieses mit aufpolymerisiertem wasserabsorbierendem Polymer/Natriumchlorid 160 g/m2 betrug.The amount of monomer solution was selected so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer / sodium chloride was 160 g / m 2 .
Die Messergebnise sind in der Tabelle 1 zusammengefasst.The measurement results are summarized in Table 1.
Beispiel 7Example 7
Es wurde verfahren wie unter Beispiel 3. Die Monomerlösung enthielt 27,8 Gew.-% Natriumacrylat, 1 ,5 Gew.-% Acrylsäure, 1 ,00 Gew.-% Polyethylenglykoldiacrylat (Diac- rylat eines Polyethylenglykols mit einer mittleren Molmasse von 400), 0,15 Gew.-% 2- Hydroxy-1-[4-(hydroxyethoxy)phenyl]- 2-methyl-1-propanon, 5,8 Gew.-% Natriumchlorid und Wasser (hergestellt aus einer Monomerlösung gemäß Beispiel 3 und 30 Gew.- %, bezogen auf die Monomerlösung gemäß Beispiel 3, einer 25 gew.-%igen wässrigen Kochsalzlösung).The procedure was as in Example 3. The monomer solution contained 27.8 wt .-% sodium acrylate, 1, 5 wt .-% acrylic acid, 1, 00 wt .-% polyethylene glycol diacrylate (diacrylate of a polyethylene glycol having an average molecular weight of 400) , 0.15 wt .-% of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] - 2-methyl-1-propanone, 5.8 wt .-% sodium chloride and water (prepared from a monomer solution according to Example 3 and 30% by weight, based on the monomer solution according to Example 3, of a 25% strength by weight aqueous sodium chloride solution).
Die Menge an Monomerlösung wurde so gewählt, dass die Beladung des Polyethylen- terephthalat-Vlieses mit aufpolymerisiertem wasserabsorbierendem Polymer/Natriumchlorid 160 g/m2 betrug.The amount of monomer solution was selected so that the loading of the polymer terephthalate non-woven with polymerized water-absorbing polymer / sodium chloride was 160 g / m 2 .
Die Messergebnise sind in der Tabelle 1 zusammengefasst.The measurement results are summarized in Table 1.
Tabelle 1 : FeuchtigkeitsaufnahmeTable 1: Moisture absorption

Claims

Patentansprüche claims
1. Feuchtigkeitsregulierende Verbundstoffe, umfassend1. Moisture-controlling composites comprising
a) mindestens ein flächiges Trägermaterial, b) mindestens eine wasserlösliche hygroskopische Substanz und c) mindestens ein in Gegenwart der Substanz b) auf das Trägermaterial a) aufpolymerisiertes wasserabsorbierendes Polymer,a) at least one planar carrier material, b) at least one water-soluble hygroscopic substance and c) at least one water-absorbing polymer grafted onto the carrier material a) in the presence of the substance b),
wobei das Verhältnis von hygroskopischer Substanz b) zu Polymer c) zwischenwherein the ratio of hygroscopic substance b) to polymer c) between
0,01 und 1 beträgt.0.01 and 1.
2. Verbundstoff gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Trägermaterial a) ein Gewebe und/oder Vlies ist.2. Composite according to claim 1, characterized in that the carrier material a) is a fabric and / or non-woven.
3. Verbundstoff gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass die relative Feuchte über einer übersättigten wässrigen Lösung der hygroskopischen Substanz b) im Gleichgewicht bei 2O0C mindestens 40% beträgt.3. Composite according to claim 1 or 2, characterized in that the relative humidity over a supersaturated aqueous solution of the hygroscopic substance b) in equilibrium at 2O 0 C is at least 40%.
4. Verbundstoff gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die hygroskopische Substanz b) ein anorganisches Salz ist.4. Composite according to one of claims 1 to 3, characterized in that the hygroscopic substance b) is an inorganic salt.
5. Verbundstoff gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Polymer c) saure Gruppen enthält.5. Composite according to one of claims 1 to 4, characterized in that the polymer c) contains acidic groups.
6. Verbundstoff gemäß Anspruch 5, dadurch gekennzeichnet, dass die sauren Gruppen zu mindestens 25 mol-% neutralisiert sind.6. Composite according to claim 5, characterized in that the acidic groups are neutralized to at least 25 mol%.
7. Verfahren zur Herstellung feuchtigkeitsregulierender Verbundstoffe, dadurch gekennzeichnet, dass eine Monomerlösung, enthaltend7. A process for the preparation of moisture-regulating composites, characterized in that a monomer solution containing
i) mindestens ein ethylenisch ungesättigtes Monomer, ii) mindestens eine wasserlösliche hygroskopische Substanz, iii) mindestens einen Vernetzer, iv) gegebenenfalls ein oder mehrere mit den unter i) genannten Monomeren copolymerisierbare ethylenisch und/oder allylisch ungesättigte Monomere und v) gegebenenfalls ein oder mehrere wasserlösliche Polymere,i) at least one ethylenically unsaturated monomer, ii) at least one water-soluble hygroscopic substance, iii) at least one crosslinker, iv) optionally one or more ethylenically and / or allylically unsaturated monomers copolymerizable with the monomers mentioned under i) and v) optionally one or more water-soluble polymers,
auf ein flächiges Trägermaterial aufgebracht und polymerisiert wird, wobei dasis applied to a sheet-like support material and polymerized, wherein the
Verhältnis von hygroskopischer Substanz ii) zu Monomer i) zwischen 0,01 und 1 beträgt. Ratio of hygroscopic substance ii) to monomer i) is between 0.01 and 1.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass das Monomer i) saure Gruppen enthält.8. The method according to claim 7, characterized in that the monomer i) contains acidic groups.
9. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, dass die sauren Gruppen zu mindestens 25 mol-% neutralisiert sind.9. The method according to claim 8, characterized in that the acidic groups are neutralized to at least 25 mol%.
10. Verfahren gemäß einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass die relative Feuchte über einer übersättigten wässrigen Lösung der hygroskopi- sehen Substanz ii) im Gleichgewicht bei 200C mindestens 40% beträgt.10. The method according to any one of claims 7 to 9, characterized in that the relative humidity over a supersaturated aqueous solution of the hygroscopic substance ii) in equilibrium at 20 0 C is at least 40%.
11. Verfahren gemäß einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass die hygroskopische Substanz ii) ein anorganisches Salz ist.11. The method according to any one of claims 7 to 10, characterized in that the hygroscopic substance ii) is an inorganic salt.
12. Verfahren gemäß einem der Ansprüche 7 bis 11 , dadurch gekennzeichnet, dass das Trägermaterial ein Gewebe und/oder Vlies ist.12. The method according to any one of claims 7 to 11, characterized in that the carrier material is a fabric and / or non-woven.
13. Verwendung von Verbundstoffen gemäß einem der Ansprüche 1 bis 6 zur Feuchtigkeitsregulierung.13. Use of composites according to any one of claims 1 to 6 for moisture regulation.
14. Sitzpolster oder Matratzen, enthaltend Verbundstoffe gemäß einem der Ansprüche 1 bis 6. 14. Seat pad or mattress comprising composite materials according to one of claims 1 to 6.
EP06725526A 2005-04-04 2006-04-03 Humidity-regulating composite materials Withdrawn EP1869246A1 (en)

Applications Claiming Priority (2)

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DE200510015536 DE102005015536A1 (en) 2005-04-04 2005-04-04 Moistures regulating composite material comprises laminar substrate, water-soluble hygroscopic substance and water-absorbing polymerized polymer, which is present on the hygroscopic substance or the laminar substrate
PCT/EP2006/061287 WO2006106096A1 (en) 2005-04-04 2006-04-03 Humidity-regulating composite materials

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