WO2007023086A1 - Verbesserte feuchtigkeitsregulierende verbundstoffe - Google Patents
Verbesserte feuchtigkeitsregulierende verbundstoffe Download PDFInfo
- Publication number
- WO2007023086A1 WO2007023086A1 PCT/EP2006/065170 EP2006065170W WO2007023086A1 WO 2007023086 A1 WO2007023086 A1 WO 2007023086A1 EP 2006065170 W EP2006065170 W EP 2006065170W WO 2007023086 A1 WO2007023086 A1 WO 2007023086A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- hygroscopic substance
- monomer
- polymer
- weight
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
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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 was therefore to provide moisture-regulating composites with good drapability.
- the object of the present invention has been achieved by moisture-regulating composites comprising
- weight ratio of hygroscopic substance b) to polymer c) is in the range of 0.01 and 1, which are characterized in that the polymer c) contains a plasticizer.
- 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.
- 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 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.
- 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. 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.
- 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, particularly preferably at least 30 ppm by weight, particularly preferably by 50 ppm by weight, hydroquinone halide, in each case based on acrylic acid, wherein acrylic acid salts are taken into account arithmetically as acrylic acid.
- acrylic acid salts are taken into account arithmetically as acrylic acid.
- 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).
- 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 ("crosslinker"), so that the polymer produced contains a corresponding proportion of the crosslinker, of course in copolymerized form 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 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 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 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-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, 15-ethoxylated glycerol or trimethylolpropane, as well as 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 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 a customary amount of, for example, 0.5 to 5.5 parts by weight, based on 100 parts by weight of monomer i). In a particularly preferred embodiment of the process, however, it is used 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 Were added at least 9 parts by weight, in each case 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, and generally, a content of at most 25 parts by weight, preferably at most 20 parts by weight, and more 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 a hygroscopic substance ii) and as a water-soluble polymer v).
- graft polymerization catalysts for example iron salts
- the polymers will serve as the graft base for the polymerization and the polymerizing monomers 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.
- Alka Ii 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 having a water content well below 50% by weight as a waxy mass having a melting point above 23 ° C present.
- 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 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 ° 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 by at least 30 0 C.
- the glass transition temperature is a known property of polymers and can be determined by the method ASTM E1356-03
- 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 glycerol and sorbitol, polyethylene glycol and their mixtures. Particularly preferred is glycerin.
- hydrocarbons and hydrocarbon niches 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 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 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 .
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Public Health (AREA)
- Emergency Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Biomedical Technology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Mattresses And Other Support Structures For Chairs And Beds (AREA)
- Polymerisation Methods In General (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2006800307437A CN101248231B (zh) | 2005-08-23 | 2006-08-09 | 改善的湿气调节复合材料 |
JP2008527430A JP5300476B2 (ja) | 2005-08-23 | 2006-08-09 | 湿分を調整する改善された複合材料 |
US11/994,517 US7790638B2 (en) | 2005-08-23 | 2006-08-09 | Humidity-regulating composite materials |
EP20060792747 EP1920105B1 (de) | 2005-08-23 | 2006-08-09 | Verbesserte feuchtigkeitsregulierende verbundstoffe |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200510039968 DE102005039968A1 (de) | 2005-08-23 | 2005-08-23 | Verbesserte feuchtigkeitsregulierende Verbundstoffe |
DE102005039968.1 | 2005-08-23 |
Publications (1)
Publication Number | Publication Date |
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WO2007023086A1 true WO2007023086A1 (de) | 2007-03-01 |
Family
ID=37084587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/065170 WO2007023086A1 (de) | 2005-08-23 | 2006-08-09 | Verbesserte feuchtigkeitsregulierende verbundstoffe |
Country Status (6)
Country | Link |
---|---|
US (1) | US7790638B2 (de) |
EP (1) | EP1920105B1 (de) |
JP (1) | JP5300476B2 (de) |
CN (1) | CN101248231B (de) |
DE (1) | DE102005039968A1 (de) |
WO (1) | WO2007023086A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009156358A1 (de) * | 2008-06-24 | 2009-12-30 | Basf Se | Verbesserte feuchtigkeitsregulierende verbundstoffe |
WO2011032862A1 (de) | 2009-09-18 | 2011-03-24 | Basf Se | Mit superabsorber ausgerüstete offenzellige schäume |
CN102041688A (zh) * | 2010-11-01 | 2011-05-04 | 张瑜 | 一种防水透气有机硅合成革及其制造方法 |
WO2011054784A1 (de) | 2009-11-06 | 2011-05-12 | Basf Se | Verbesserte superabsorber enthaltende textilien |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005015536A1 (de) * | 2005-04-04 | 2006-10-05 | Basf Ag | Feuchtigkeitsregulierende Verbundstoffe |
DE102013003755A1 (de) * | 2013-03-06 | 2014-09-11 | Carl Freudenberg Kg | Belüftungseinsatz |
CN109051340B (zh) * | 2018-06-29 | 2020-10-02 | 上海衡元高分子材料有限公司 | 环境湿度调节物品 |
CN108816006A (zh) * | 2018-06-29 | 2018-11-16 | 上海衡元高分子材料有限公司 | 用于调节环境湿度的组合物 |
CN108842509B (zh) * | 2018-06-29 | 2020-11-10 | 上海衡元高分子材料有限公司 | 环境湿度调节物品制造方法 |
CN108824075B (zh) * | 2018-06-29 | 2020-11-10 | 上海衡元高分子材料有限公司 | 环境湿度调节物品制造方法 |
WO2020001619A1 (zh) * | 2018-06-29 | 2020-01-02 | 上海衡元高分子材料有限公司 | 涂布液、环境湿度调节物品及其制造方法 |
CN108816005A (zh) * | 2018-06-29 | 2018-11-16 | 上海衡元高分子材料有限公司 | 用于调节环境湿度的组合物 |
CN108486951A (zh) * | 2018-06-29 | 2018-09-04 | 上海衡元高分子材料有限公司 | 环境湿度调节物品制造方法 |
CN115418863B (zh) * | 2022-10-13 | 2024-05-24 | 佛山市顺德区阿波罗环保器材有限公司 | 湿度调节用复合材料及其制备方法和湿度调节设备 |
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- 2006-08-09 CN CN2006800307437A patent/CN101248231B/zh not_active Expired - Fee Related
- 2006-08-09 JP JP2008527430A patent/JP5300476B2/ja not_active Expired - Fee Related
- 2006-08-09 WO PCT/EP2006/065170 patent/WO2007023086A1/de active Application Filing
- 2006-08-09 EP EP20060792747 patent/EP1920105B1/de not_active Not-in-force
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---|---|---|---|---|
WO2009156358A1 (de) * | 2008-06-24 | 2009-12-30 | Basf Se | Verbesserte feuchtigkeitsregulierende verbundstoffe |
WO2011032862A1 (de) | 2009-09-18 | 2011-03-24 | Basf Se | Mit superabsorber ausgerüstete offenzellige schäume |
WO2011054784A1 (de) | 2009-11-06 | 2011-05-12 | Basf Se | Verbesserte superabsorber enthaltende textilien |
CN102041688A (zh) * | 2010-11-01 | 2011-05-04 | 张瑜 | 一种防水透气有机硅合成革及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1920105A1 (de) | 2008-05-14 |
JP2009506226A (ja) | 2009-02-12 |
CN101248231A (zh) | 2008-08-20 |
DE102005039968A1 (de) | 2007-03-08 |
US20080194162A1 (en) | 2008-08-14 |
CN101248231B (zh) | 2011-12-28 |
EP1920105B1 (de) | 2015-03-25 |
US7790638B2 (en) | 2010-09-07 |
JP5300476B2 (ja) | 2013-09-25 |
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