EP1920104A1 - Improved humidity-regulating composite materials - Google Patents

Improved humidity-regulating composite materials

Info

Publication number
EP1920104A1
EP1920104A1 EP06792746A EP06792746A EP1920104A1 EP 1920104 A1 EP1920104 A1 EP 1920104A1 EP 06792746 A EP06792746 A EP 06792746A EP 06792746 A EP06792746 A EP 06792746A EP 1920104 A1 EP1920104 A1 EP 1920104A1
Authority
EP
European Patent Office
Prior art keywords
water
hygroscopic substance
monomer
weight
parts
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Withdrawn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
EP06792746A
Other languages
German (de)
French (fr)
Inventor
Mirjam Herrlich-Loos
Corinna Haindl
Samantha Champ
Martin Beck
Markus Tönnessen
Michael Fastner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1920104A1 publication Critical patent/EP1920104A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47C—CHAIRS; SOFAS; BEDS
    • A47C21/00—Attachments for beds, e.g. sheet holders, bed-cover holders; Ventilating, cooling or heating means in connection with bedsteads or mattresses
    • A47C21/04—Devices for ventilating, cooling or heating
    • A47C21/042—Devices for ventilating, cooling or heating for ventilating or cooling
    • A47C21/046—Devices for ventilating, cooling or heating for ventilating or cooling without active means, e.g. with openings or heat conductors
    • 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 System
    • 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
    • D06M11/32—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
    • 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
    • D06M11/51—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 System
    • 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
    • D06M11/58—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
    • 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
    • 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
    • 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
    • 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
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • 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
    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • the present invention relates to improved moisture controlling composites, processes for their preparation and their use for moisture control.
  • 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 01/56625, EP-A 1 178 149 and US 5,962,068 describe processes for producing water-absorbing composites in which water-absorbing polymers are polymerized onto a carrier material.
  • WO 00/64311 discloses composites wherein water-absorbing polymers have been polymerized onto a support material. The composites are used for moisture regulation in seat cushions.
  • WO 2004/067826 A1 teaches multilayer textile fabrics, in particular those of single-sided mesh-coated nonwovens, which may contain functional agents such as, for example, water-absorbing polymers.
  • JP-A 05-105705 relates to non-flowing dry center I, consisting of a support material and hygroscopic salts, wherein the hygroscopic salts are fixed by means of water-absorbing polymers on the support material.
  • German Patent Application DE 10 2005 015 536.7 describes moisture-regulating composites which comprise at least one planar support material, at least one water-soluble hygroscopic substance and at least one water-absorbing polymer grafted onto the support material in the presence of the water-soluble hygroscopic substance.
  • the known moisture-controlling composites are often relatively stiff and the contained particles of water-absorbing polymers are relatively hard. In the further processing and use of the composites, this stiffness can cause difficulties, the drapability of the composites suffers.
  • the most commonly used to avoid transpiration unpleasant effects are used - with larger amounts of liquid than is usually produced by transpiration (for example, when spilling liquid on such equipped seating o car seats) unwanted bumps whose reformation by drying takes longer than the usual drying of the moisture-regulating composites.
  • the object of the present invention has been achieved by moisture-regulating composites comprising
  • ratio of hygroscopic substance b) to polymer c) is in the range of 0.01 to 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 01/56625 on page 16, line 40, to page 20, line 27, or mixed forms of fabrics and nonwovens, as disclosed, for example, in WO 2004/067826.
  • Suitable carrier materials a) are, for example, woven or nonwoven fabrics 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 crossed-fiber products, preferably fibers crossed 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 consolidated nonwovens are obtainable, for example, by bonding the fibers with liquid binders or by melting binder fibers which have been added to the nonwoven during manufacture.
  • Cohesively consolidated nonwovens are, 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 800 g / m 2 , preferably from 50 to 600 g / m 2 , particularly preferably from 100 to 500 g / m 2 .
  • Hygroscopic substances b) are substances capable of absorbing water vapor, that is, water vapor from the air condenses on the hygroscopic substance, increasing the water content of the hygroscopic substance b).
  • 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 20 ° C. in equilibrium a relative humidity of less than 95%, preferably less than 90%, preferably less than 85%, particularly preferably less than 80% , and of 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 partial pressure of water vapor and water vapor pressure multiplied by 100%.
  • the hygroscopic substance b) is distributed in the polymerized-on water-absorbing polymer.
  • the moisture-regulating composites of the invention can be obtained by polymerization of a monomer solution containing
  • the weight ratio of hygroscopic substance ii) to monomer i) is preferably at most, in particular less than 0.8, preferably at most, in particular less than 0.6, particularly preferably at most, in particular less than 0.5, very particularly preferably at most, in particular 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.
  • Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
  • the monomers i), in particular acrylic acid preferably contain up to
  • 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.
  • 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, particularly preferably around 50 ppm by weight, hydroquinone hemether, in each case on acrylic acid, wherein acrylic acid salts are mathematically accounted for as acrylic acid with.
  • an acrylic acid having a corresponding content of hydroquinone half-ether can be used.
  • hygroscopic substances ii) which can be used in the process according to the invention have already been described above as hygroscopic substances b).
  • crosslinker 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 diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A 530 438.
  • 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 and also trimethylolpropane triacrylate 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-A 343 427.
  • crosslinkers iii) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol di- and glycerol triallyl ethers, polyallyl 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-fold mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-fold ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, trimethylolpropane lethanes 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 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.
  • the crosslinker is added to the monomer solution in an amount of at least 6 parts by weight, preferably at least 7 parts by weight, more preferably at least 8 parts by weight, and most preferably at least 9 parts by weight based on the 100 parts by weight of monomer i).
  • the upper limit of the content of crosslinking agent in the monomer is less critical, generally a content of at most 25 parts by weight, preferably at most 20 parts by weight, and most preferably, at most 18 parts by weight is set.
  • suitable crosslinker contents are at least 10 parts by weight, at least 10.5 parts by weight, at least 11 parts by weight, at least 11.5 parts by weight, at least 12 parts by weight, at least 12.5 parts by weight. Parts, at least 13 parts by weight based on 100 parts by weight of monomer i).
  • 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 hygroscopic substance ii) and as 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 -%, wherein the usual neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal hydrogencarbonates and mixtures thereof.
  • the usual neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal hydrogencarbonates and mixtures thereof.
  • alkali metal salts it is also possible to use ammonium salts.
  • Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
  • 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.
  • an initiator can be used to accelerate or control the start of the polymerization reaction, in which case it is possible to use any known initiator or initiator system in the usual way.
  • the polymers c) contain at least one plasticizer, which is added to the monomer solution before the polymerization and remains in the polymer.
  • plasticizer is understood as meaning a substance which lowers the glass transition temperature of the polymer c) in the amount used
  • the plasticizer in the amount to be used lowers the glass transition temperature of the polymer by at least 2 ° C., preferably at least 4 0 C, particularly preferably by at least 6 ° C and in a particularly preferred manner at least 10 0 C from.
  • a plasticizer is added in an amount that the glass transition temperature of the polymer by at least 20 0 C, or at least 30 0 C
  • the glass transition temperature is a known property of polymers and can be measured by the method ASTM E1356-03 "Standard Test Method for Assignment of the Glass Transition Temperature by Differential Scanning Calorimetry" or the equivalent standard ISO 11357-2.
  • plasticizers are liquid at room temperature and are also solvents or dispersants for the polymer. If the polymer is produced from the monomer by UV irradiation, a plasticizer which is sufficiently stable against UV light must be chosen, which in addition does not disturb the UV-induced polymerization.
  • the plasticizer is hydrophilic and immiscible with water indefinitely.
  • Suitable plasticizers are, for example, alcohols, polyalcohols, such as glycerol and sorbitol, glycols and ether glycols, such as mono- or diethers of polyalkylene glycols, mono- or diesters of polyalkylene glycols, polyethylene glycols, polypropylene glycols, mixed polyethylene and propylene glycols, glycolates, glycerol, sorbitan esters, and citric acid. and tartaric acid esters or imidazoline-derived amphoteric surfactants.
  • preferred Plasticizers are polyalcohols such as glycerine and sorbitol, polyethylene glycol and their mixtures. Particularly preferred is glycerin.
  • hydrocarbons and hydrocarbon mixtures such as white oil, in particular medicinal white oil or liquid paraffin.
  • the plasticizer is usually added in an amount sufficient to achieve the desired glass transition temperature reduction.
  • Typical levels of plasticizer are 5 to 50 parts by weight, preferably 8 to 40 parts by weight, in particular 10 to 30 parts by weight of plasticizer, based on 100 parts by weight of monomer i).
  • 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 of the invention can optimally release the absorbed moisture in phases of non-use and regenerate quickly.
  • the composites according to the invention enable a hitherto unattainable sitting or lying comfort.
  • the composites are stored for 60 minutes at a temperature of 23 0 C and a relative humidity of 50% in the climate chamber for equilibrium. Subsequently, the relative humidity is increased to 90% and the composites for 90 minutes at 30 0 C maintained (absorption phase). The relative humidity is then reduced to 40% and the sample is kept at 40 ° C. for 100 minutes (desorption phase).
  • the weight change by absorption / desorption is measured continuously and as an increase in weight, based on g applied substance (water-absorbing polymer and / or salt).
  • the reference point for weight gain is the weight after equilibration after 60 minutes.
  • a monomer solution was sprayed and cured by UV radiation for 2 minutes. It was then dried for 5 minutes at 90 ° C. in a countercurrent dryer.
  • the monomer solution contained 19599 g of a 37.5% strength by weight aqueous sodium acrylate solution (corresponding to 24.5% by weight of sodium acrylate in the entire monomer solution), 435 g of acrylic acid (8.5% by weight), 900 g of polyethylene glycol diacrylate (Diacrylate of a polyethylene glycol having an average molecular weight of 400) (3% by weight) as a crosslinker, 66 g of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone (0, 22 wt .-%) as an initiator, 1500 g of glycerol [5 wt .-%) and 7500 g of a 25 wt .-% aqueous sodium chloride solution (6.25 wt .-% NaCl).
  • 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 .

Abstract

The invention relates to improved 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, and which is obtained by poymerising a monomer mixture which contains at least one ethylenically unsaturated monomer i) and at least 6 weight parts of cross-linking agents iii) in relation to 100 weight parts of monomers i) The invention also relates to a method for producing said materials and to the use thereof for humidity regulation.

Description

Verbesserte feuchtigkeitsregulierende VerbundstoffeImproved moisture-regulating composites
Beschreibungdescription
Die vorliegende Erfindung betrifft verbesserte feuchtigkeitsregulierende Verbundstoffe, Verfahren zu ihrer Herstellung sowie deren Verwendung zur Feuchtigkeitsregulierung.The present invention relates to improved moisture controlling composites, processes for their preparation and their use for moisture control.
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.
Der Stand der Technik zur Herstellung wasserabsorbierender Polymere wird bei- spielsweise in der Monographie "Modern Superabsorbent Polymer Technology", F. L. Buchholz und AT. Graham, Wiley-VCH, 1998, Seiten 69 bis 117, zusammenfassend beschrieben.The state of the art for producing water-absorbing polymers is described, for example, in the monograph "Modern Superabsorbent Polymer Technology", F.L. Buchholz and AT. Graham, Wiley-VCH, 1998, pages 69 to 117, in summary.
WO 01/56625, EP-A 1 178 149 und US 5,962,068 beschreiben Verfahren zur Herstel- lung wasserabsorbierender Verbundstoffe, bei denen wasserabsorbierende Polymere auf ein Trägermaterial auf polymerisiert werden.WO 01/56625, EP-A 1 178 149 and US 5,962,068 describe processes for producing water-absorbing composites in which water-absorbing polymers are polymerized onto a carrier material.
Die WO 00/64311 offenbart Verbundstoffe bei denen wasserabsorbierende Polymere auf ein Trägermaterial polymerisiert wurden. Die Verbundstoffe werden zur Feuchtig- keitsregulierung in Sitzpolstern verwendet. WO 2004/067826 A1 lehrt mehrschichtige textile Flächengebilde, insbesondere solche aus einseitig maschenbeschichteten Vliesstoffen, die Funktionsmittel wie zum Beispiel wasserabsorbierende Polymere enthalten können.WO 00/64311 discloses composites wherein water-absorbing polymers have been polymerized onto a support material. The composites are used for moisture regulation in seat cushions. WO 2004/067826 A1 teaches multilayer textile fabrics, in particular those of single-sided mesh-coated nonwovens, which may contain functional agents such as, for example, water-absorbing polymers.
JP-A 05-105705 betrifft nichtzerfließende Trocken mitte I, bestehend aus einem Trägermaterial und hygroskopischen Salzen, wobei die hygroskopischen Salze mittels wasserabsorbierender Polymere auf dem Trägermaterial fixiert werden. Die ältere deutsche Patentanmeldung mit dem Aktenzeichen DE 10 2005 015 536.7 beschreibt feuchtigkeitsregulierende Verbundstoffe, die mindestens ein flächiges Trägermaterial, mindestens eine wasserlösliche hygroskopische Substanz und mindestens ein in Gegenwart der wasserlöslichen hygroskopischen Substanz auf das Trägermate- rial aufpolymerisiertes wasserabsorbierendes Polymer enthalten.JP-A 05-105705 relates to non-flowing dry center I, consisting of a support material and hygroscopic salts, wherein the hygroscopic salts are fixed by means of water-absorbing polymers on the support material. German Patent Application DE 10 2005 015 536.7 describes moisture-regulating composites which comprise at least one planar support material, at least one water-soluble hygroscopic substance and at least one water-absorbing polymer grafted onto the support material in the presence of the water-soluble hygroscopic substance.
Die bekannten feuchtigkeitsregulierenden Verbundstoffe sind häufig relativ steif und die enthaltenen Partikel wasserabsorbierender Polymere sind relativ hart. Bei der Weiterverarbeitung und Verwendung der Verbundstoffe können durch diese Steifheit Schwie- rigkeiten auftreten, die Drapierfähigkeit der Verbundstoffe leidet. Zudem können sich bei lokalem Kontakt derartiger feuchtigkeitsregulierender Verbundstoffe - die meist zur Vermeidung mit Transpiration verbundener unangenehmer Effekte verwendet werden - mit größeren Mengen Flüssigkeit als gängigerweise durch Transpiration erzeugt wird (beispielsweise beim Verschütten von Flüssigkeit auf derart ausgestatte Sitzmöbel o- der Autositze) unerwünschte Unebenheiten bilden, deren Rückbildung durch Trocknung länger dauert als das übliche Trocknen der feuchtigkeitsregulierenden Verbundstoffe.The known moisture-controlling composites are often relatively stiff and the contained particles of water-absorbing polymers are relatively hard. In the further processing and use of the composites, this stiffness can cause difficulties, the drapability of the composites suffers. In addition, in local contact of such moisture-regulating composites - the most commonly used to avoid transpiration unpleasant effects are used - with larger amounts of liquid than is usually produced by transpiration (for example, when spilling liquid on such equipped seating o car seats) unwanted bumps whose reformation by drying takes longer than the usual drying of the moisture-regulating composites.
Aufgabe der vorliegenden Erfindung war daher die Bereitstellung feuchtigkeitsregulie- render Verbundstoffe, die reversibel große Mengen Wasserdampf aufnehmen können, ohne bei Kontakt mit größeren Mengen Flüssigkeit unerwünschte Unebenheiten zu bilden.It was therefore an object of the present invention to provide moisture-regulating composites which can reversibly absorb large amounts of water vapor without forming undesired unevenness on contact with relatively large amounts of liquid.
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, erhältlich durch Polymerisation einer Monomerlösung enthaltend mindestens ein ethylenisch ungesättigtes Monomer i) und mindestens 6 Gew.-Teile Vernetzer iii) bezogen auf 100 Gew. -Teile Monomer i),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) obtainable by polymerization of a monomer solution containing at least one ethylenically unsaturated monomer i) and at least 6 parts by weight of crosslinker iii) based on 100 parts by weight of monomer i),
wobei das Verhältnis von hygroskopischer Substanz b) zu Polymer c) im Bereich von 0,01 bis 1 liegt.wherein the ratio of hygroscopic substance b) to polymer c) is in the range of 0.01 to 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. Die Trägermaterialien a) unterliegen keiner Beschränkung. Bevorzugte Trägermateria- lien sind Gewebe und/oder Vliese, wie in der WO 01/56625 auf Seite 16, Zeile 40, bis Seite 20, Zeile 27, beschrieben werden, oder Mischformen aus Geweben und Vliesen wie beispielsweise in WO 2004/067826 offenbart.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 01/56625 on page 16, line 40, to page 20, line 27, or mixed forms of fabrics and nonwovens, as disclosed, for example, in WO 2004/067826.
Geeignete Trägermaterialien a) sind beispielsweise Gewebe oder Vliese aus synthetischen 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, mo- difizierte Zellulosen, wie Zelluloseacetat. Weiterhin können auch Gemische obengenannter polymeren Materialien eingesetzt werden.Suitable carrier materials a) are, for example, woven or nonwoven fabrics 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 Fasern, vorzugsweise rechtwinklig gekreuzten Fasern.Fabrics are crossed-fiber products, preferably fibers crossed 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 Bindemitteln oder durch Schmelzen von Bindefasern, die dem Vlies bei der Herstellung zugesetzt wurden. Kohäsiv verfestigte Vliese sind beispielsweise durch Anlösen der Fasern mit geeigneten Chemikalien und Anwendung von Druck.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 consolidated nonwovens are obtainable, for example, by bonding the fibers with liquid binders or by melting binder fibers which have been added to the nonwoven during manufacture. Cohesively consolidated nonwovens are, for example, by dissolving the fibers with suitable chemicals and applying pressure.
Die Trägermaterialien weisen zweckmäßigerweise ein Flächengewicht von 20 bis 800 g/m2, vorzugsweise von 50 bis 600 g/m2, besonders bevorzugt von 100 bis 500 g/m2, auf.The support materials advantageously have a weight per unit area of from 20 to 800 g / m 2 , preferably from 50 to 600 g / m 2 , particularly preferably from 100 to 500 g / m 2 .
Hygroskopische Substanzen b) sind Stoffe, die in der Lage sind Wasserdampf zu absorbieren, 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. Hygroskopische 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, increasing the water content of the hygroscopic substance b). 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 200C 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 20 ° C. in equilibrium a relative humidity of less than 95%, preferably less than 90%, preferably less than 85%, particularly preferably less than 80% , and of 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 Wasserdampf partialdruck und Wasserdampf- druck multipliziert mit 100%.The relative humidity is the quotient of partial pressure of water vapor and water vapor pressure multiplied by 100%.
Vorzugsweise liegt die hygroskopische Substanz b) im aufpolymerisierten 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.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 humidity does not further increase the seating comfort.
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 wasserlösliche hygroskopische Substanz, iii) mindestens 6 Gew.-Teile eines Vernetzers, bezogen auf 100 Gew. -Teile Monomer i), 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 water-soluble hygroscopic substance, iii) at least 6 parts by weight of a crosslinker, based on 100 parts by weight of monomer i), iv) optionally one or more of those mentioned under i) Monomeric copolymerizable ethylenically and / or allylic unsaturated monomers and v) optionally one or more water-soluble polymers,
welche auf ein Trägermaterial aufgebracht und polymerisiert wird, erhalten werden, wobei das Gewichtsverhältnis von hygroskopischer Substanz ii) zu Monomer i) im Bereich von 0,01 bis 1 liegt.which is applied to a support material and polymerized, can be obtained, wherein the weight ratio of hygroscopic substance ii) to monomer i) is in the range of 0.01 to 1.
Das Gewichtsverhältnis von hygroskopischer Substanz ii) zu Monomer i) beträgt vorzugsweise höchstens, insbesondere weniger als 0,8, bevorzugt höchstens, insbesondere weniger als 0,6, besonders bevorzugt höchstens, insbesondere weniger als 0,5, ganz besonders bevorzugt höchstens, insbesondere weniger als 0,4, und mindestens 0,05, bevorzugt mindestens 0,1 , besonders bevorzugt mindestens 0,15.The weight ratio of hygroscopic substance ii) to monomer i) is preferably at most, in particular less than 0.8, preferably at most, in particular less than 0.6, particularly preferably at most, in particular less than 0.5, very particularly preferably at most, in particular 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 Acrylsäure. Die Monomere i), insbesondere Acrylsäure, enthalten vorzugsweise bis zuSuitable 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. The monomers i), in particular acrylic acid, preferably contain up to
0,025 Gew.-% eines Hydrochinonhalbethers. Bevorzugte Hydrochinonhalbether sind0.025 wt .-% of a Hydrochinonhalbethers. Preferred hydroquinone half ethers
Hydrochinonmonomethylether (MEHQ) und/oder Tocopherole.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 physiologisch verträgliche Carbonsäuren. Die Carbonsäuren können Mono-, Di- oder Tricar- bonsäuren sein.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.
Bevorzugt ist alpha-Tocopherol mit R1 = R2 = R3 = Methyl, insbesondere racemisches alpha-Tocopherol. R4 ist besonders bevorzugt Wasserstoff oder Acetyl. Insbesondere bevorzugt ist RRR-alpha-Tocopherol.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, Hydrochinonhalbether, jeweils bezogen auf Acrylsäure, wobei Acrylsäuresalze rechnerisch als Ac- rylsäure mit berücksichtigt werden. Beispielsweise kann zur Herstellung der Monomerlösung eine Acrylsäure mit einem entsprechenden 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, particularly preferably around 50 ppm by weight, hydroquinone hemether, in each case on acrylic acid, wherein acrylic acid salts are mathematically accounted for as acrylic acid with. For example, to prepare the monomer solution, an acrylic acid having a corresponding content of hydroquinone half-ether can be used.
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 („Vernetzer"), durchge- führt, so dass das hergestellte Polymer einen entsprechenden Anteil des Vernetzers enthält, selbstverständlich in einpolymerisierter Form. Geeignete Vernetzer iii) sind beispielsweise Ethylenglykoldimethacrylat, Diethylenglykoldiacrylat, Allylmethacrylat, Trimethylolpropantriacrylat, Triallylamin, Tetraallyloxyethan, wie in EP-A 530 438 be- schrieben, Di- und Triacrylate, wie in EP-A 547 847, EP-A 559 476, EP-A 632 068, WO 93/21237, WO 03/104299, WO 03/104300, WO 03/104301 und in DE-A 103 31 450 beschrieben, gemischte Acrylate, die neben Acrylatgruppen weitere ethylenisch ungesättigte Gruppen enthalten, wie in DE-A 103 314 56 und der älteren deutschen Anmeldung mit dem Aktenzeichen 103 55 401.7 beschrieben, oder Vernetzermischungen, wie beispielsweise in DE-A 195 43 368, DE-A 196 46 484, WO 90/15830 und WO 02/32962 beschrieben.The water-absorbing polymers are crosslinked, ie 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 ("crosslinker"), so that the polymer produced contains a corresponding fraction of the crosslinker, Suitable crosslinkers iii) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A 530 438. di-and triacrylates, as described in EP-A 547 847, EP-A 559 476, EP-A 632 068, WO 93/21237, WO 03/104299, WO 03/104300, WO 03/104301 and DE-A A 103 31 450, mixed acrylates containing in addition to acrylate groups further ethylenically unsaturated groups, as described in DE-A 103 314 56 and the prior German application with the file number 103 55 401.7, or crosslinker mixtures, such as in DE-A 195 43 368, DE-A 196 46 484, WO 90/15830 and WO 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 Trimethylolpropantriacrylat und Allylverbindungen, wie Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraallylo- xyethan, Triallylamin, Tetraallylethylendiamin, Allylester der Phosphorsäure sowie Vi- nylphosphonsäurederivate, wie sie beispielsweise in EP-A 343 427 beschrieben sind. Weiterhin geeignete Vernetzer iii) sind Pentaerythritoldi-, Pentaerythritoltri- und Pen- taerythritoltetraallylether, Polyethylenglykoldiallylether, Ethylenglykoldiallylether, Glyze- rindi- und Glyzerintriallylether, Polyallylether auf Basis Sorbitol, sowie ethoxylierte Varianten davon. Im erfindungsgemäßen Verfahren einsetzbar sind Di(meth)acrylate von Polyethylenglykolen, wobei das eingesetzte Polyethylenglykol ein Molekulargewicht zwischen 300 und 1000 aufweist.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 and also trimethylolpropane triacrylate 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-A 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 ethers, polyallyl 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.
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 Glyzerins 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, Trimethylo- lethans oder Trimethylolpropans.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-fold mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-fold ethoxylated glycerol or trimethylolpropane, and at least 40-times ethoxylated glycerol, trimethylolpropane lethanes 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 03/104301 beschrieben sind. Besonders vor- teilhaft 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 wasseraborbierenden Polymer aus und die wässrigen Extrakte der damit hergestellten wasserabsorbierenden Polymere weisen eine fast unveränderte Oberflächenspannung (typischerweise mindestens 0,068 N/m) im Vergleich zu Wasser gleicher Temperatur auf. Der Vernetzer wird erfindungsgemäß der Monomerlösung in einer Menge von mindestens 6 Gew.-Teile, vorzugsweise mindestens 7 Gew. -Teile, in besonders bevorzugter Weise mindestens 8 Gew.-Teile und in ganz besonders bevorzugter Weise mindestens 9 Gew.-Teile zugegeben, jeweils bezogen auf die 100 Gew.-Teile Monomer i). Die O- bergrenze des Gehalts an Vernetzer im Monomer ist weniger kritisch, im Allgemeinen wird ein Gehalt von höchstens 25 Gew.-Teile, vorzugsweise höchstens 20 Gew.-Teile und in besonders bevorzugter Weise von höchstens 18 Gew.-Teile eingestellt. Beispiele geeigneter Vernetzergehalte sind mindestens 10 Gew.-Teile, mindestens 10,5 Gew.- Teile, mindestens 11 Gew.-Teile, mindestens 11 ,5 Gew.-Teile, mindestens 12 Gew.- Teile, mindestens 12,5 Gew.-Teile, mindestens 13 Gew.-Teile bezogen auf 100 Gew.- Teil Monomer i).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 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 characterized by particularly low residual contents (typically below 10 ppm by weight) in the water-absorbent 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 at the same temperature. According to the invention, the crosslinker is added to the monomer solution in an amount of at least 6 parts by weight, preferably at least 7 parts by weight, more preferably at least 8 parts by weight, and most preferably at least 9 parts by weight based on the 100 parts by weight of monomer i). The upper limit of the content of crosslinking agent in the monomer is less critical, generally a content of at most 25 parts by weight, preferably at most 20 parts by weight, and most preferably, at most 18 parts by weight is set. Examples of suitable crosslinker contents are at least 10 parts by weight, at least 10.5 parts by weight, at least 11 parts by weight, at least 11.5 parts by weight, at least 12 parts by weight, at least 12.5 parts by weight. Parts, at least 13 parts by weight based on 100 parts by weight of monomer i).
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 hygrosko- pische Substanz ii) als auch als wasserlösliches Polymer v) eingesetzt werden.Hygroscopic polymers, such as soluble polyacrylic acids, can be used both as hygroscopic substance ii) and as 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.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.
Die Säuregruppen der bevorzugten Monomere i) sind üblicherweise teilweise neutrali- siert, 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 ver- wendet 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.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 -%, wherein the usual neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal hydrogencarbonates and mixtures thereof. Instead of alkali metal salts, it is also possible to use ammonium salts. 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 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. Wie üblich bei derartigen Polymerisationsreaktionen kann zur Beschleunigung oder Kontrolle des Starts der Polymerisationsreaktion ein Initiator verwendet werden, hier ist die Verwendung jedes bekannten Initiators oder Initiatorsystems in üblicher weise möglich.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. As usual in such polymerization reactions, an initiator can be used to accelerate or control the start of the polymerization reaction, in which case it is possible to use any known initiator or initiator system in the usual way.
In einer bevorzugten Ausführungsform der Erfindung enthalten die Polymere c) mindestens einen Weichmacher, der der Monomerlösung vor der Polymerisation zugesetzt wird und im Polymeren verbleibt. Unter „Weichmacher" wird im Zusammenhang mit dieser Erfindung eine Substanz verstanden, die in der angewendeten Menge die Glasübergangstemperatur des Polymeren c) absenkt. Im Allgemeinen senkt der Weichmacher in der zu verwendenden Menge die Glasübergangstemperatur des Polymeren um mindestens 2 0C, vorzugsweise mindestens 4 0C, in besonders bevorzugter Weise um mindestens 6°C und in ganz besonders bevorzugter Weise um mindestens 10 0C ab. Beispielsweise wird ein Weichmacher in einer Menge zugesetzt, die die Glasübergangstemperatur des Polymeren um mindestens 20 0C oder um mindestens 300C absenkt. Die Glasübergangstemperatur ist eine bekannte Eigenschaft von Polymeren und kann nach der Methode ASTM E1356-03 „Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry" oder der äquivalenten Norm ISO 11357-2 gemessen werden.In a preferred embodiment of the invention, the polymers c) contain at least one plasticizer, which is added to the monomer solution before the polymerization and remains in the polymer. In the context of this invention, "plasticizer" is understood as meaning a substance which lowers the glass transition temperature of the polymer c) in the amount used In general, the plasticizer in the amount to be used lowers the glass transition temperature of the polymer by at least 2 ° C., preferably at least 4 0 C, particularly preferably by at least 6 ° C and in a particularly preferred manner at least 10 0 C from. for example, a plasticizer is added in an amount that the glass transition temperature of the polymer by at least 20 0 C, or at least 30 0 C The glass transition temperature is a known property of polymers and can be measured by the method ASTM E1356-03 "Standard Test Method for Assignment of the Glass Transition Temperature by Differential Scanning Calorimetry" or the equivalent standard ISO 11357-2.
Übliche Weichmacher sind bei Raumtemperatur flüssig und sind auch Lösungs- oder Dispersionsmittel für das Polymere. Sofern das Polymere durch UV-Bestrahlung aus dem Monomeren erzeugt wird, ist ein gegen UV-Licht ausreichend stabiler Weichmacher zu wählen, der zudem die UV-induzierte Polymerisation nicht stört. Vorzugsweise ist der Weichmacher hydrophil und mit Wasser unbegrenzt mischbar. Geeignete Weichmacher sind beispielsweise Alkohole, Polyalkohole wie Glycerin und Sorbit, GIy- kole und Etherglykole wie Mono- oder Diether von Polyalkylenglykolen, Mono- oder Diester von Polyalkylengklykolen, Polyethylenglykole, Polypropylenglykole, gemischte Polyethylen- und Propylenglyklole, Glykolate, Glycerol, Sorbitanester, Zitronen- und Weinsäureester oder vom Imidazolin abgeleitete amphotere Tenside. Bevorzugte Weichmacher sind Polyalkohole wie Glycerin und Sorbit, Polyethylenglykol und ihre Mischungen. Besonders bevorzugt ist Glycerin.Conventional plasticizers are liquid at room temperature and are also solvents or dispersants for the polymer. If the polymer is produced from the monomer by UV irradiation, a plasticizer which is sufficiently stable against UV light must be chosen, which in addition does not disturb the UV-induced polymerization. Preferably, the plasticizer is hydrophilic and immiscible with water indefinitely. Suitable plasticizers are, for example, alcohols, polyalcohols, such as glycerol and sorbitol, glycols and ether glycols, such as mono- or diethers of polyalkylene glycols, mono- or diesters of polyalkylene glycols, polyethylene glycols, polypropylene glycols, mixed polyethylene and propylene glycols, glycolates, glycerol, sorbitan esters, and citric acid. and tartaric acid esters or imidazoline-derived amphoteric surfactants. preferred Plasticizers are polyalcohols such as glycerine and sorbitol, polyethylene glycol and their mixtures. Particularly preferred is glycerin.
Als Weichmacher auch geeignet sind Kohlenwasserstoffe und Kohlenwasserstoffgemi- sehe wie Weißöl, insbesondere medizinisches Weißöl oder Flüssigparaffin.Also suitable as plasticizers are hydrocarbons and hydrocarbon mixtures, such as white oil, in particular medicinal white oil or liquid paraffin.
Der Weichmacher wird üblicherweise in einer Menge zugesetzt, die zum Erreichen der gewünschten Absenkung der Glasübergangstemperatur ausreicht. Typische Gehalte an Weichmacher sind 5 - 50 Gew.-Teile, bevorzugt 8 - 40 Gew.-Teile, insbesondere 10 - 30 Gew.-Teile Weichmacher bezogen auf 100 Gew.-Teile Monomer i).The plasticizer is usually added in an amount sufficient to achieve the desired glass transition temperature reduction. Typical levels of plasticizer are 5 to 50 parts by weight, preferably 8 to 40 parts by weight, in particular 10 to 30 parts by weight of plasticizer, based on 100 parts by weight of monomer i).
Die erfindungsgemäßen Verbundstoffe eignen sich vorzüglich zur Feuchtigkeitsregulierung, 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 erfindungsgemäßen Verbundstoffe die aufgenommene Feuchtigkeit in Phasen der Nichtbenutzung optimal wieder abgeben und sich schnell regenerieren. Aufgrund dieses aus- gewogenen 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 of the invention can optimally release the absorbed moisture in phases of non-use and regenerate quickly. On account of this balanced property profile, the composites according to the invention enable a hitherto unattainable sitting or lying comfort.
Methoden:methods:
Bestimmung der FeuchtigkeitsaufnahmeDetermination of moisture absorption
Die Verbundstoffe werden 60 Minuten bei einer Temperatur von 23 0C und einer relativen Luftfeuchtigkeit von 50% im Klimaschrank zur Gleichgewichtseinstellung gelagert. Anschließend wird die relative Luftfeuchtigkeit auf 90% erhöht und die Verbundstoffe für 90 Minuten bei 30 0C gehalten(Absorptionsphase). Danach wird die relative Luftfeuchtigkeit auf 40 % gesenkt und die Probe für 100 Minuten bei 40 0C gehalten (De- sorptionsphase).The composites are stored for 60 minutes at a temperature of 23 0 C and a relative humidity of 50% in the climate chamber for equilibrium. Subsequently, the relative humidity is increased to 90% and the composites for 90 minutes at 30 0 C maintained (absorption phase). The relative humidity is then reduced to 40% and the sample is kept at 40 ° C. for 100 minutes (desorption phase).
Die Gewichtsänderung durch Absorption/Desorption wird kontinuierlich gemessen und als Gewichtszunahme, bezogen auf g aufgebrachter Substanz (wasserabsorbierendes Polymer und/oder Salz). Bezugspunkt für die Gewichtszunahme ist das Gewicht nach Gleichgewichtseinstellung nach 60 Minuten. BeispieleThe weight change by absorption / desorption is measured continuously and as an increase in weight, based on g applied substance (water-absorbing polymer and / or salt). The reference point for weight gain is the weight after equilibration after 60 minutes. Examples
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. Anschließend 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. It was then dried for 5 minutes at 90 ° C. in a countercurrent dryer.
Die Monomerlösung enthielt 19599 g einer 37,5 Gew.-%igen wässrigen Natriumacrylat- lösung (entsprechend 24,5 Gew.-% Natriumacrylat in der gesamten Monomerlösung), 435 g Acrylsäure (8,5 Gew.-%), 900 g Polyethylenglykoldiacrylat (Diacrylat eines PoIy- ethylenglykols mit einer mittleren Molmasse von 400) (3 Gew.-%) als Vernetzer, 66 g 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]- 2-methyl-1-propanon (0,22 Gew.-%) als Initiator, 1500 g Glycerin [5 Gew.-%) und 7500 g einer 25 Gew.-%igen wässrigen Natrium- Chloridlösung (6,25 Gew.-% NaCI).The monomer solution contained 19599 g of a 37.5% strength by weight aqueous sodium acrylate solution (corresponding to 24.5% by weight of sodium acrylate in the entire monomer solution), 435 g of acrylic acid (8.5% by weight), 900 g of polyethylene glycol diacrylate (Diacrylate of a polyethylene glycol having an average molecular weight of 400) (3% by weight) as a crosslinker, 66 g of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone (0, 22 wt .-%) as an initiator, 1500 g of glycerol [5 wt .-%) and 7500 g of a 25 wt .-% aqueous sodium chloride solution (6.25 wt .-% NaCl).
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 .

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, erhältlich durch Polymerisation einer Monomerlösung, enthaltend mindestens ein ethylenisch ungesättigtes Monomer i) und mindestens 6 Gew. -Teile Vernetzer iii) bezogen auf 100 Gew. -Teile Monomer i),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) obtainable by polymerization of a monomer solution containing at least one ethylenically unsaturated monomer i) and at least 6 parts by weight of crosslinking agent iii) based on 100 parts by weight of monomer i),
wobei das Gewichtsverhältnis von hygroskopischer Substanz b) zu Polymer c) im Bereich von 0,01 bis 1 liegt.wherein the weight ratio of hygroscopic substance b) to polymer c) is in the range of 0.01 to 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 rela- tive Feuchte über einer übersättigten wässrigen Lösung der hygroskopischen3. Composite according to claim 1 or 2, characterized in that the relative humidity over a supersaturated aqueous solution of the hygroscopic
Substanz b) im Gleichgewicht bei 200C mindestens 40% beträgt.Substance b) in equilibrium at 20 ° 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 6 Gew.-Teile eines Vernetzers, bezogen auf 100 Gew. -Teilei) at least one ethylenically unsaturated monomer, ii) at least one water-soluble hygroscopic substance, iii) at least 6 parts by wt. of a crosslinker, based on 100 parts by wt
Monomer i), 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, auf ein flächiges Trägermaterial aufgebracht und polymerisiert wird, wobei das Gewichtsverhältnis von hygroskopischer Substanz ii) zu Monomer i) im Bereich von 0,01 bis 1 liegt.I), 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, is applied to a flat support material and polymerized, wherein the weight ratio of hygroscopic substance ii) to monomer i) is in the range of 0.01 to 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 Grup- pen 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 hygroskopischen 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.
EP06792746A 2005-08-23 2006-08-09 Improved humidity-regulating composite materials Withdrawn EP1920104A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005039974A DE102005039974A1 (en) 2005-08-23 2005-08-23 Improved moisture-regulating composites
PCT/EP2006/065169 WO2007023085A1 (en) 2005-08-23 2006-08-09 Improved humidity-regulating composite materials

Publications (1)

Publication Number Publication Date
EP1920104A1 true EP1920104A1 (en) 2008-05-14

Family

ID=37442010

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06792746A Withdrawn EP1920104A1 (en) 2005-08-23 2006-08-09 Improved humidity-regulating composite materials

Country Status (6)

Country Link
US (1) US20080214725A1 (en)
EP (1) EP1920104A1 (en)
JP (1) JP5145230B2 (en)
CN (1) CN101248230B (en)
DE (1) DE102005039974A1 (en)
WO (1) WO2007023085A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005015536A1 (en) * 2005-04-04 2006-10-05 Basf Ag 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
ITMI20072087A1 (en) * 2007-10-30 2009-04-30 Getters Spa METHOD FOR THE PRODUCTION OF A COMPOSITE ABSORBER FOR THE REMOVAL OF H2O CONSISTED OF DISSOLVED HYGROSCOPIC SALTS IN A POLYMERIC MATRIX
JP5717449B2 (en) * 2008-02-27 2015-05-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Multilayer composite material, method for producing the same, and method for using the same
JP5818797B2 (en) 2009-09-18 2015-11-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Open-cell foam with superabsorbent
EP2496343A1 (en) 2009-11-06 2012-09-12 Basf Se Textiles comprising improved superabsorbers
EP2438983A1 (en) 2010-10-08 2012-04-11 SAES GETTERS S.p.A. Dispensable polymeric precursor composition for transparent composite sorber materials
DE102013003755A1 (en) * 2013-03-06 2014-09-11 Carl Freudenberg Kg ventilation insert
NO2697473T3 (en) * 2014-01-13 2018-07-07
JP6704315B2 (en) * 2016-08-24 2020-06-03 帝人フロンティア株式会社 Fiber structure and method for manufacturing the same
CN109051340B (en) * 2018-06-29 2020-10-02 上海衡元高分子材料有限公司 Article for regulating environmental humidity

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4127337A1 (en) * 1990-08-29 1992-03-05 Volkswagen Ag Motor vehicle seat - has upholstery contg. absorbent polymer or super-absorbent hydrogel which dissipates body moisture
JP3146030B2 (en) * 1991-10-17 2001-03-12 株式会社日本触媒 Preparation of composites containing deliquescent inorganic salts
JP3583227B2 (en) * 1995-06-19 2004-11-04 三菱化学株式会社 Water-absorbing composite and method for producing the same
US20030008591A1 (en) * 2001-06-18 2003-01-09 Parsons John C. Water dispersible, salt sensitive nonwoven materials
DE102005015536A1 (en) * 2005-04-04 2006-10-05 Basf Ag 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007023085A1 *

Also Published As

Publication number Publication date
DE102005039974A1 (en) 2007-03-22
JP5145230B2 (en) 2013-02-13
CN101248230B (en) 2012-07-25
US20080214725A1 (en) 2008-09-04
JP2009506148A (en) 2009-02-12
CN101248230A (en) 2008-08-20
WO2007023085A1 (en) 2007-03-01

Similar Documents

Publication Publication Date Title
EP1920105B1 (en) Improved humidity-regulating composite materials
EP1920104A1 (en) Improved humidity-regulating composite materials
EP1869246A1 (en) Humidity-regulating composite materials
DE69629081T2 (en) Absorbent composite material, absorbent article and process for their manufacture
EP0862590B1 (en) Fluid-absorbing polymers, process for the preparation and use thereof
EP2046403B1 (en) Method for producing water-absorbent polymer particles with a higher permeability by polymerising droplets of a monomer solution
EP2046401B1 (en) Method for producing water-absorbent polymer particles with a higher permeability by polymerising droplets of a monomer solution
DE19529348C2 (en) Absorbent for water and aqueous liquids based on polyacrylate and process for their production and use
DE10043710B4 (en) Use of powdery postcrosslinked polymers and hygiene articles
DE2749386A1 (en) DISPERSIONS OF HYDROPHILIC ACRYLIC RESINS
WO2006077054A1 (en) Method for producing polymers by means of spray polymerisation
EP2478050B1 (en) Open-cell foams equipped with superabsorbers
JPH06507452A (en) fiber or filament
EP2046839A1 (en) Method for producing water-absorbent polymer particles with a higher permeability by polymerising droplets of a monomer solution
WO2011054784A1 (en) Textiles comprising improved superabsorbers
US3743536A (en) Nonwoven sponge fabric
EP1487882B1 (en) Base polymer obtained by hydrogenation
WO2009156358A1 (en) Improved moisture-regulating composite materials
WO2008077781A1 (en) Use of fiber compounds as artificial snow

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080325

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20100128

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: D06M 11/13 20060101ALI20130806BHEP

Ipc: D06M 11/64 20060101ALI20130806BHEP

Ipc: A47C 21/04 20060101ALI20130806BHEP

Ipc: D06N 3/04 20060101ALI20130806BHEP

Ipc: C08J 7/04 20060101ALI20130806BHEP

Ipc: D06M 13/148 20060101ALI20130806BHEP

Ipc: D06M 15/21 20060101ALI20130806BHEP

Ipc: D06M 11/56 20060101ALI20130806BHEP

Ipc: A61F 13/00 20060101ALI20130806BHEP

Ipc: D06M 11/48 20060101ALI20130806BHEP

Ipc: D06M 15/263 20060101AFI20130806BHEP

Ipc: D06M 13/17 20060101ALI20130806BHEP

INTG Intention to grant announced

Effective date: 20130829

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HERRLICH-LOOS, MIRJAM

Inventor name: CHAMP, SAMANTHA

Inventor name: TOENNESSEN, MARKUS

Inventor name: FASTNER, MICHAEL

Inventor name: BECK, MARTIN

Inventor name: HAINDL, CORINNA

STAA Information on the status of an ep patent application or granted ep patent

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

18D Application deemed to be withdrawn

Effective date: 20140110