WO2006042704A2 - Feinteilige wasserabsorbierende polymerpartikel mit hoher flüssigkeitstransport- und absorptionsleistung - Google Patents
Feinteilige wasserabsorbierende polymerpartikel mit hoher flüssigkeitstransport- und absorptionsleistung Download PDFInfo
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- WO2006042704A2 WO2006042704A2 PCT/EP2005/011073 EP2005011073W WO2006042704A2 WO 2006042704 A2 WO2006042704 A2 WO 2006042704A2 EP 2005011073 W EP2005011073 W EP 2005011073W WO 2006042704 A2 WO2006042704 A2 WO 2006042704A2
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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- Finely divided water-absorbing polymer particles with high liquid transport and absorption performance Finely divided water-absorbing polymer particles with high liquid transport and absorption performance
- the present invention relates to finely divided water-absorbing polymer particles having high liquid transport and absorption performance, to processes for their preparation and to the use in hygiene articles and packaging materials.
- 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 the production of diapers, tampons, sanitary napkins and other hygiene articles, but also as water-retaining agents in agricultural horticulture.
- water-absorbing polymer particles are generally postcrosslinked. This postcrosslinking can be carried out in aqueous gel phase.
- ground and sieved polymer particles base polymer
- Crosslinkers suitable for this purpose are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the hydrophilic polymer.
- US 5,599,335 discloses that coarser particles have a higher liquid conductivity (SFC) of the swollen gel layer. Furthermore, it is taught that the liquid conductivity (SFC) can be increased by post-crosslinking, but always the centrifuge retention capacity (CRC) and thus the absorption capacity of the water-absorbing polymer particles decreases.
- SFC liquid conductivity
- CRC centrifuge retention capacity
- WO 04/069404 discloses salt-resistant water-absorbing polymer particles which each have similar values for absorption under pressure (AUL) and centrifuge retention capacity (CRC).
- AUL absorption under pressure
- CRC centrifuge retention capacity
- WO 04/069915 describes a process for the preparation of water-absorbent polymer particles with high liquid conductivity (SFC), which at the same time have strong capillary forces, i. which can absorb aqueous liquids against gravity.
- SFC liquid conductivity
- the capillary action of the polymer particles is achieved by a special surface texture. For this purpose, particles having a size of less than 180 .mu.m are screened out of the base polymer, agglomerated and combined with the previously separated particles of greater than 180 .mu.m.
- a further object was the provision of optimized water-absorbing polymer particles having a low average particle diameter.
- a further object was a process for producing water-absorbing polymer particles having a high centrifuge retention capacity (CRC), high absorption under pressure (AUL), high active (wick absorption) and passive liquid transport (Fluid transfer), wherein the water-absorbing polymers in particular should have a high fluid transfer (SFC).
- CRC centrifuge retention capacity
- AUL high absorption under pressure
- AUL high active
- wick absorption passive liquid transport
- SFC fluid transfer
- Another object has been to provide a process for making water-absorbent polymer particles which produces white polymer particles that are free of noticeable odors, particularly when loaded with liquid.
- the object is achieved by providing water-absorbing polymer particles containing
- centrifuge retention capacity is at least 26 g / g
- absorption under a pressure of 4.83 kPa is at least 23 g / g
- transport value is at least 15,000 cm 3 s
- TW transport value
- wick absorption after 60 minutes is the amount by weight of 0.9% by weight saline, which absorbs 70 g of the water-absorbing polymer particles in 60 minutes, during which the water-absorbing polymer particles in a circular vessel with an inner diameter of 6 cm, which is closed at the bottom with a sieve bottom of mesh size 36 ⁇ m, and the sieve bottom is in contact with 0.9% by weight saline solution without pressure.
- centrifuge retention capacity is determined according to the test method No. 441.2-02 "Centrifuge Retention Capacity" recommended by EDANA (European Dispo- sables and Nonwovens Association).
- the absorption under pressure is determined according to the test method No. 442.2-02 "Absorption under pressure" recommended by the EDANA (European Disposables and Nonwovens Association).
- the transport value (TW) is preferably at least 17,500 cm 3 s, preferably at least 20,000 cm 3 s, particularly preferably at least 22,500 cm 3 s, very particularly preferably at least 25,000 cm 3 s, and usually not more than 100,000 cm 3 s.
- the polymer particles Preferably, less than 2 wt .-%, more preferably less than 1, 5 wt .-%, most preferably less than 1 wt .-%, the polymer particles have a particle size of less than 150 microns.
- the particle size is determined according to the test method No. 420.2-02 "Particle size distribution" recommended by EDANA (European Disposables and Nonwovens Association).
- the acid groups of the copolymerized monomer a) are preferably greater than 60 mol%, preferably greater than 61 mol%, more preferably greater than 62 mol%, very particularly preferably greater than 63 mol%, and preferably not greater than 70 mol%. %, preferably at most 69 mol%, particularly preferably at most 68 mol%, very particularly preferably at most 67 mol%, neutralized.
- Suitable monomers for the copolymerized monomers a), b) and c) are the monomers i), ii) and iii) described below.
- Suitable water-soluble polymers for the at least partially grafted water-soluble polymers d) are the water-soluble polymers iv) described below.
- Suitable postcrosslinkers for the reacted postcrosslinkers e) are the postcrosslinkers v) described below.
- the water content of the water-absorbing polymer particles according to the invention is preferably less than 6% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight.
- Preferred water-absorbing polymer particles according to the invention are polymer particles A, B and C having the abovementioned properties.
- the polymer particles A has a particle size of about 600 microns.
- At least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, most preferably at least 99% by weight, of the polymer particles A has a particle size of 150 to 600 ⁇ m.
- At least 70 wt .-%, preferably at least 80 wt .-%, more preferably at least 85 wt .-%, most preferably at least 90 wt .-%, of the polymer particles A has a particle size of 300 to 600 microns.
- the centrifuge retention capacity (CRC) of the polymer particles A is usually at least 26 g / g, preferably at least 27 g / g, preferably at least 28 g / g, more preferably at least 29 g / g, most preferably at least 30 g / g, and usually not over 50g / g.
- the absorption under a pressure of 4.83 kPa (AULOJpsi) of the polymer particles A is usually at least 23 g / g, preferably at least 24 g / g, preferably at least 25 g / g, more preferably at least 26 g / g, very particularly preferably at least 27 g / g, and usually not more than 45 g / g.
- the saline flow conductivity (SFC) of the polymer particles A is usually min ⁇ least 80x10 "7 cm 3 sec / g, preferably at least 90x10" 7 cm 3 sec / g, preferably mindes ⁇ least 100x10 "7 cm 3 sec / g, more preferably at least 120x10 '7 cm 3 s / g and at least 150x10 particularly preferably' 7 cm 3 s / g, and typically not more than 500x10 "7 cm 3 s / g.
- the polymer particle B has a particle size of about 850 microns.
- At least 90 wt .-%, preferably at least 95 wt .-%, more preferably at least 98 wt .-%, most preferably at least 99 wt .-%, of the polymer particles B has a particle size of 150 to 850 microns.
- the polymer particles B usually have at least 16 wt .-%, preferably at least 17 wt .-%, preferably at least 18 wt .-%, more preferably at least 19 wt .-%, most preferably at least 20 wt. %, a particle size of less than 300 microns.
- the centrifuge retention capacity (CRC) of the polymer particles B is usually more than 28 g / g, at least 29 g / g, preferably at least 30 g / g, preferably at least 31 g / g, more preferably at least 32 g / g, very particularly preferably at least 33 g / g, and usually not more than 50 g / g.
- the absorption under a pressure of 4.83 kPa (AUL0.7 psi) of the polymer particles B is usually at least 23 g / g, preferably at least 24 g / g, more preferably at least 25 g / g, particularly preferably at least 26 g / g, very particularly preferably at least 27 g / g, and usually not more than 45 g / g.
- the saline flow conductivity (SFC) of the polymer particles B is usually min ⁇ least 45x10 "7 cm 3 sec / g, preferably at least 50x10" 7 cm 3 sec / g, preferably mindes ⁇ least 60x10 "7 cm 3 sec / g, more preferably at least 70x10 '7 cm 3 s / g, most preferably at least 80x10 ' 7 cm 3 s / g, and usually not more than 500x10 "7 cm 3 s / g.
- the polymer particles B are coated with a water-insoluble metal phosphate.
- Insoluble in water means a solubility of less than 1 g, preferably of less than 0.1 g, more preferably less than 0.01 g, in 100 ml of water at 25 ° C.
- Suitable water-insoluble metal phosphates are, for example, phosphates which can be regarded in the technical sense as' "phosphates", such as phosphate oxides, phosphate hydroxides, phosphate silicates, phosphate fluorides or the like.
- Preferred water-insoluble metal phosphates are pyrophosphates, hydrogen phosphates and phosphates of calcium, magnesium, strontium, barium, zinc, iron, aluminum, titanium, zirconium, hafnium, tin, cerium, scandium, yttrium or lanthanum, and mixtures thereof.
- Preferred phosphates are calcium hydrogen phosphate, calcium phosphate, apatite, Thomas flour, Berlinite and Rhenaniaphosphat. Particularly preferred are calcium hydrogen phosphate, calcium phosphate and apatite, the term apatite meaning fluoro, hydroxy, chloro, carbonate or carbonate fluoroapatite. Of course, mixtures of various water-insoluble metal phosphates were ⁇ used.
- the proportion of the water-insoluble metal phosphate is usually from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, particularly preferably from 0.05 to 2.5% by weight, based on the water-absorbing polymer particles B.
- the centrifuge retention capacity (CRC) of the water-insoluble metal phosphates coated polymer particles B is usually more than 29 g / g, at least 30 g / g, preferably at least 31 g / g, preferably at least 32 g / g, particularly preferably at least 33 g / g , very particularly preferably at least 34 g / g, and usually not more than 50 g / g.
- the absorption under a pressure of 4.83 kPa (AUL0.7 psi) of the water-insoluble metal phosphates coated polymer particles B is usually at least 23 g / g, preferably at least 24 g / g, preferably at least 25 g / g, more preferably at least 26 g / g, very particularly preferably at least 27 g / g, and usually not more than 45 g / g.
- the saline flow conductivity (SFC) of the be ⁇ with water-insoluble metal phosphates coated polymer particles B is usually at least 45x10 "r cm 3 s / g, vor ⁇ preferably at least 50x10" 7 cm 3 sec / g, preferably at least 60x10 "7 cm 3 s / g, particularly preferably at least 70x10 "7 cm 3 sec / g, most preferably at least 80x10" 7 cm 3 sec / g, and typically not more than 500x10 "7 cm 3 s / g.
- Polymer Particles C are usually at least 45x10 "r cm 3 s / g, vor ⁇ preferably at least 50x10" 7 cm 3 sec / g, preferably at least 60x10 "7 cm 3 s / g, particularly preferably at least 70x10 "7 cm 3 sec / g, most preferably at least 80x10" 7 cm 3 sec / g, and typically not more than 500x10 "7 cm 3 s
- the polymer particles C Preferably, less than 2 wt .-%, more preferably less than 1.5 wt .-%, most preferably less than 1 wt .-%, the polymer particles C have a particle size of about 850 microns.
- At least 90 wt .-%, preferably at least 95 wt .-%, more preferably at least 98 wt .-%, most preferably at least 99 wt .-%, of the polymer particles C has a particle size of 150 to 850 microns.
- the polymer particles C are usually less than 15 wt .-%, preferably less than 14 wt .-%, preferably less than 13 wt .-%, more preferably less than 12 wt .-%, most preferably less as 11 wt .-%, a particle size of less than 300 microns.
- the centrifuge retention capacity (CRC) of the polymer particles C is usually at least 30 g / g, preferably at least 31 g / g, preferably at least 32 g / g, more preferably at least 33 g / g, most preferably at least 34 g / g, and usually not over 50g / g.
- the absorption under a pressure of 4.83 kPa (AUL0.7 psi) of the polymer particles C is usually at least 23 g / g, preferably at least 24 g / g, more preferably at least 25 g / g, particularly preferably at least 26 g / g, very particularly preferably at least 27 g / g, and usually not more than 45 g / g.
- the saline flow conductivity (SFC) of the polymer particles C is usually min ⁇ least 45x10 -7 cm 3 s / g, preferably at least 50x10 "7 cm 3 sec / g, preferably mindes ⁇ least 60x10" 7 cm 3 sec / g, more preferably at least 70x10 '7 cm 3 s / g, most preferably at least 80x10 "7 cm 3 s / g, and usually not more than 500x10 " 7 cm 3 s / g.
- Another object of the present invention is a process for the preparation of water-absorbing polymers by polymerization of a monomer solution, enthal ⁇ tend
- TW transport value
- wick absorption after 60 minutes is the amount by weight of 0.9% by weight sodium chloride solution, which absorbs 70 g of the water-absorbing polymer particles in 60 minutes, the water-absorbing polymer particles being in a circular shape during the measurement Container with a réelle ⁇ diameter of 6 cm are located, which is closed at the bottom with a sieve bottom of Ma ⁇ mesh size 36 microns, and the bottom of the sieve is pressureless with 0.9% by weight saline in contact.
- 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 acrylic acid.
- the water-absorbing polymers are crosslinked, i. the polymerization is carried out in the presence of compounds having at least two polymerisable groups which can be radically copolymerized into the polymer network.
- Suitable crosslinkers ii) 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 the German patent application with the file reference 103 31 450.4 described, mixed acrylates which in addition to acrylate groups further ethylenically unsaturated Grup ⁇ pen contain, as in German Patent Applications Nos. 103 31 456.3 and 103 55401.7
- Suitable crosslinkers ii) 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 also nylphosphonklarivate, as described for example in EP-A 343 427.
- crosslinkers ii) are pentaerythritol di-pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol di- and 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, where the polyethylene glycol used has a molecular weight between 300 and 1000.
- crosslinkers ii) are di- and triacrylates of 3 to 15 times ethoxylated glycerol, of 3 to 15 times ethoxylated trimethylolpropane, in particular di- and triacrylates of 3-ethoxylated glycerol or trimethylolpropane, of also propoxylated glycerol or trimethylolpropane, as well as the 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-fold ethoxylated glycerol or trimethylolpropane, and the 40-times ethoxylated glycerol or trimethylolpropane.
- Very particularly preferred crosslinkers ii) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in German Patent Application DE 103 19 462.2.
- Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
- 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 glycerol.
- Examples of ethylenically unsaturated monomers iii) copolymerizable with the monomers i) are acrylamide, methacrylamide, crotonamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate.
- water-soluble polymers iv) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
- a suitable base polymer and further suitable hydrophilic ethylenically unsaturated monomers i) are described in DE-A 199 41 423, EP-A 686 650, WO 01/45758 and WO 03/104300.
- the reaction is preferably carried out in a kneader, as described, for example, in WO 01/38402, or on a belt reactor, as described, for example, in EP-A 955 086.
- the acid groups of the hydrogels obtained are preferably greater than 60 mol%, preferably greater than 61 mol%, more preferably greater than 62 mol%, very particularly preferably greater than 63 mol%, and preferably not greater than 70 mol%. %, preferably at most 69 mol%, particularly preferably at most 68 mol%, very particularly preferably at most 67 mol%, neutralized, it being possible to use the customary neutralizing agents, for example ammonia, amines, such as ethanolamine , Diethanolamine, triethanolamine or dimethylaminoethanolamine, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal hydrogencarbonates and mixtures thereof, with sodium and potassium being particularly preferred as alkali metals, but most preferably sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
- the neutralization is achieved by mixing in the neutralizing agent as an aqueous solution or preferably also as a solid.
- the neutralization can be carried out after the polymerization at the hydrogel stage. However, it is also possible to neutralize up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, of the acid groups prior to the polymerization by adding a part of the neutralizing agent already to the monomer solution and only after the desired degree of final neutralization is adjusted after the polymerization at the level of the hydrogel.
- the monomer solution can be neutralized by mixing in the neutralizing agent, either to a predetermined degree of pre-neutralization with subsequent post-neutralization to the final value after or during the polymerization reaction, or the monomer solution is adjusted directly to the final value by mixing the neutralizing agent before the polymerization.
- the hydrogel can be mechanically comminuted, for example by means of a meat grinder, wherein the neutralizing agent can be sprayed, sprinkled or poured on and then thoroughly mixed.
- the gel mass obtained can be further gewolfft for homogenization.
- the neutralized hydrogel is then dried with a belt, fluidized bed, shaft or drum dryer until the residual moisture content is preferably below 10% by weight, in particular below 5% by weight, the water content being determined according to the method described by EDA-NA (European Disposables and Nonwovens Association) recommended test method no. 430.2-02 "Moisture content" is determined.
- the dried hydrogel is subsequently ground and sieved, with mill stands, pin mills or vibratory mills usually being used for grinding, whereby sieves are used with mesh widths necessary for the production of the water-absorbing polymer particles A, B and C.
- Suitable post-ethers v) are compounds which contain at least two groups which can form covalent bonds with the carboxylate groups of the polymers.
- Suitable compounds are, for example, alkoxysilyl compounds, polyaziridines, polyamines, polyaminediamines, di- or polyglycidyl compounds, as described in EP-A 083 022, EP-A 543 303 and EP-A 937 736, polyhydric alcohols, as in DE-C 33 14 019,
- compounds having mixed functionality such as glycidol, 3-ethyl-3-oxetanemethanol (trimethylol propane oxetane), as described in EP-A 1 199 327, aminoethanol, diethanolamine, triethanolamine or compounds which have a further function after the first reaction ⁇ form, such as ethylene oxide, propylene oxide, isobutylene oxide, aziridine, azetidine or oxetane.
- DE-A 198 07 992 bis- and poly-2-oxazolidones in DE-A 198 54 573 2-oxotetrahydro-1,3-oxazine and its derivatives, in DE-A 198 54 574 N-acyl-2-oxazolidones, in DE-A 102 04 937 cyclic ureas, in the German patent application with the file number 103 34 584.1 bicyclic amide acetals, in EP-A 1 199 327 oxetanes and cyclic ureas and in WO 03/031482 morpholine-2,3-dione and its derivatives as suitable postcrosslinkers v) described.
- the postcrosslinking is usually carried out so that a solution of the postcrosslinker is sprayed onto the hydrogel or the dry base polymer particles. After spraying, the mixture is thermally dried, wherein the post-crosslinking reaction can take place both before and during drying.
- Preferred postcrosslinkers v) are amide acetals or carbamic esters of the general formula I.
- R 1 is C 1 -C 12 -alkyl C 2 -C 12 1-hydroxyalkyl, C 2 -C 12 alkenyl or C 6 -C 12 aryl,
- R 3 is hydrogen, C r C 12 alkyl, C 2 -C 12 hydroxyalkyl, C 2 -C 12 -alkenyl or C 6 -C 12 -aryl, or X,
- R 5 is hydrogen, C r C 12 alkyl, C 2 -C 12 hydroxyalkyl, C 2 -C 12 alkenyl, C 1 -C 12 -acyl or C 6 -C 12 aryl,
- R 6 is C 1 -C 12 -alkyl, C 2 -C 2 -hydroxyalkyl, C 2 -C 12 -alkenyl or C 6 -C-
- X is a common carbonyl oxygen for the radicals R 2 and R 3
- R 1 and R 4 and / or R 5 and R 6 may be a bridged C 2 -C 6 alkanediyl, and wherein the abovementioned radicals R 1 to R 6 still have a total of one to two free valencies and with these free valences can be connected to at least one suitable basic body,
- polyhydric alcohols wherein the polyhydric alcohol preferably has a molecular weight of less than 100 g / mol, preferably less than 90 g / mol, more preferably less than 80 g / mol, most preferably less than 70 g / mol , per hydroxyl group as well as no vicinal, geminal, secondary or tertiary hydroxyl groups, and polyhydric alcohols either diols of general formula IIa
- R 6 is either an unbranched dialkyl radical of the formula - (CH 2 ) n -, where n is an integer from 3 to 20, preferably 3 to 12, where 4 is less preferred, meaning tet and both hydroxyl groups are terminal, or R 6 denotes an unbranched, branched or cyclic dialkyl radical, or polyols of the general formula IIb
- radicals R 7 , R 8 , R 9 , R 10 independently of one another are hydrogen, hydroxyl, hydroxymethyl, hydroxyethyl oxymethyl, 1-hydroxyprop-2-yloxymethyl, 2-hydroxypropyloxymethyl, methyl, ethyl, n-propyl, isopropyl, n- Butyl, n-pentyl, n-hexyl, 1, 2-dihydroxyethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl and a total of 2, 3, or 4, preferably 2 or 3, hydroxyl groups are present, and not more than one of the radicals R 7 , R 8 , R 9 , or R 10 is hydroxyl, are
- R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl, and n is either 0 or 1 .
- R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl
- R 25 represents a single bond, a linear, branched or cyclic C r C 12 -dialkyl radical, or a polyalkoxydiyl radical which is composed of one to ten ethylene oxide and / or propylene oxide units, such as, for example, polyglycol dicarboxylic acids
- the preferred postcrosslinkers v) are extremely selective. Secondary and subsequent reactions which lead to volatile and thus malodorous compounds are mini ⁇ mized. The water-absorbing polymers prepared with the preferred postcrosslinkers v) are therefore odorless even when moistened.
- epoxy compounds can undergo various rearrangement reactions at high temperatures and in the presence of suitable catalysts, which, for example, lead to aldehydes or ketones. These can then undergo further subsequent reactions, which ultimately form malodorous impurities that are undesirable because of their odor in hygiene articles. Therefore, epoxy compounds above a temperature of about 140 to 150 ° C less suitable for Nachver ⁇ netting. In the case of postcrosslinkers v) containing amino or imino groups, even more inconvenient rearrangement reactions occur at similar temperatures, as a result of which slightly foul-smelling trace impurities and brownish product discolorations occur.
- Polyhydric alcohols as postcrosslinkers v) require high postcrosslinking temperatures due to their low reactivity.
- alcohols having vicinal, geminal, secondary and tertiary hydroxyl groups form undesired by-products which lead to unpleasant odors and / or discoloration of the relevant hygiene article during manufacture or use.
- Preferred postcrosslinkers v) of the general formula I are 2-oxazolidones, such as 2-oxazolidone and N-hydroxyethyl-2-oxazolidone, N-methyl-2-oxazolidone, N-acyl-2-oxazolidones, such as N-acetyl-2-oxazolidone , 2-Oxotetrahydro-1,3-oxazine, bicyclic amidacetals, such as 5-methyl-1-aza-4,6-dioxa-bicyclo [3.3.0] octane, 1-aza-4,6-dioxabicyclo [3.3.0] octane and 5-isopropyl-1-aza-4,6-dioxa-bicyclo [3.3.0] octane, bis-2-oxazolidones and poly-2-oxazolidones.
- 2-oxazolidones such as 2-oxazolidone and N-hydroxyethyl-2-o
- Particularly preferred postcrosslinkers v) of the general formula I are 2-oxazolidone, N-methyl-2-oxazolidone, N-hydroxyethyl-2-oxazolidone and N-hydroxypropyl-2-oxazolidone.
- Preferred postcrosslinkers v) of the general formula IIa are 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol and 1,7-heptanediol. Further examples of postcrosslinkers of formula IIa are 1, 3-butanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol.
- the diols IIa are preferably water-soluble, wherein the diols of the general formula IIa at 23 ° C to at least 30 wt .-%, preferably at least 40 wt .-%, more preferably at least 50 wt .-%, most preferably mindes ⁇ least to 60 wt .-%, in water, such as 1, 3-propanediol and 1, 7-heptanediol. Even more preferred are those postcrosslinkers which are liquid at 25 ° C.
- Preferred postcrosslinkers v) of the general formula IIb are butane-1, 2,3-triol, butane-1,2,4-triol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, per molecule 1 to 3-fold ethoxylated glycerol, trimethylolethane or trimethylolpropane and per mole lekül 1- to 3-fold propoxylated glycerol, trimethylolethane or trimethylolpropane.
- 2-fold ethoxylated or propoxylated neopentyl glycol Particularly preferred are 2-fold and 3-fold ethoxylated glycerol and trimethylolpropane.
- Preferred polyhydric alcohols IIa and IIb have, at 23 0 C a viscosity of we ⁇ niger than 3000 mPas, preferably less than 1500 mPas, preferably less than 1000 mPas, particularly preferably less than 500 mPas, most preferably less than 300 mPas.
- Particularly preferred postcrosslinkers v) of the general formula III are ethylene carbonate and propylene carbonate.
- a particularly preferred postcrosslinker v) of the general formula IV is 2,2'-bis (2-oxazoline).
- the at least one postcrosslinker v) is typically present in an amount of at most 0.30% by weight, preferably at most 0.15% by weight, particularly preferably from 0.001 to 0.095% by weight, based in each case on the base polymer , used as aqueous solution.
- the aqueous postcrosslinker solution may typically also contain a cosolvent.
- cosolvents are C 1 -C 6 -alkyl, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or 2-methyl-1-propanol, C 2 -C 5 - DJoils, such as ethylene glycol, 1,2-propylene glycol or 1,4-butanediol, ketones, such as acetone, or carboxylic acid esters, such as ethyl acetate.
- a disadvantage of many of these cosolvents is that they have typical odors.
- the cosolvent itself is ideally not a post-crosslinker under the reaction conditions. However, in the limiting case and depending on residence time and temperature, it may happen that the cosolvent partially contributes to crosslinking. This is in particular the case when the postcrosslinker v) is relatively inert and can therefore itself form its cosolvent, as for example when using cyclic carbonates of the general formula III, diols of the general formula IIa or polyols of the general formula IIb .
- Such postcrosslinkers v) can also be used as cosolvents in a mixture with more reactive crosslinkers v), since the actual postcrosslinking reaction can then be carried out at lower temperatures and / or shorter residence times than in the absence of the more reactive crosslinker v).
- the diols of the general formula IIa, the polyols of the general formula IIb, and the cyclic carbonates of the general formula III are also suitable as cosolvents. They fulfill this function in the presence of a reactive postcrosslinker v) of the general formula I and / or IV and / or of a di- or tri-glycidyl crosslinker.
- preferred cosolvents in the process according to the invention are, in particular, the diols of the general formula IIa, in particular if the hydroxyl groups are hindered sterically by neighboring groups on a reaction.
- reaction-inert diols are also diols with tertiary hydroxyl groups.
- Examples of such sterically hindered and therefore particularly preferred as cosolvent diols of the general formula IIa are 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1, 3-hexanediol, 2-methyl 1, 3-propanediol and 2,4-dimethylpentane-2,4-diol.
- co-solvents in the process according to the invention are the polyols of the general formula IIb.
- the 2- to 3-fold alkoxylated polyols are especially preferred.
- especially suitable as co-solvents are also 3- to 15-fold, very particularly 5- to 10-fold ethoxylated polyols based on glycerol, trimethylolpropane, trimethylolethane or pentaerythritol.
- Particularly suitable is 7-times ethoxylated trimethylolpropane.
- cosolvents are di (trimethylolpropane) and 5-ethyl-1,3-dioxane-5-methanol.
- Particularly preferred combinations of less reactive postcrosslinker v) as the co-solvent and reactive postcrosslinker v) are combinations of preferred polyhydric alcohols, diols of the general formula IIa and polyols of the general formula IIb, with amide acetals or carbamic esters of the general formula I.
- Very particularly preferred combinations are 2-oxazolidone / 1,3-propanediol and N- (2-hydroxyethyl) -2-oxazolidone / 1,3-propanediol.
- the at least one postcrosslinker v) preferably has a boiling point of 160 0 C höchs ⁇ least 1 more preferably of more than 140 0 C, most preferably not exceeding 120 0 C, or preferably a boiling point of at least 200 0 C, particularly preferably of at least 220 ° C, most preferably at least 250 ° C.
- the cosolvent preferably has a boiling point of at most 16O 0 C, more preferably of at most 140 0 C, most preferably of at most 120 0 C, or preferably a boiling point of at least 200 0 C, more preferably of at least 220 0 C, most preferably of at least 25O 0 C.
- cosolvents are also those which form a low-boiling azeotrope with water or a second cosolvent.
- the boiling point of this azeotrope is at most 160 0 C, more preferably at most 14O 0 C, most preferably at most 120 0 C.
- steam-volatile cosolvents as they are completely or partially removed with the evaporating water during drying.
- the concentration of the cosolvent in the aqueous postcrosslinker solution is from 15 to 50% by weight, preferably from 15 to 40% by weight, particularly preferably from 20 to 35% by weight, based on the postcrosslinker solution.
- concentration of the cosolvent in the aqueous postcrosslinker solution is from 15 to 50% by weight, preferably from 15 to 40% by weight, particularly preferably from 20 to 35% by weight, based on the postcrosslinker solution.
- no cosolvent is used.
- the at least one postcrosslinker v) is then used only as a solution in water, optionally with the addition of a deagglomerating auxiliary.
- the concentration of at least one Nachvemetzers v) in the aqueous Nachver ⁇ network solution for example, 1 to 20 wt .-%, preferably 1, 5 to 10% by weight, particularly preferably 2 to 5 wt .-%, based on the Nachvernetzerates ,
- the total amount of the postcrosslinker solution based on the base polymer is usually from 0.3 to 15% by weight, preferably from 2 to 6% by weight.
- the base polymer is a surfactant as
- Deagglomerationstosmittel for example sorbitan monoesters, such as sorbitan monococoate and sorbitan monolaurate, or added ethoxylated variants thereof.
- Other very suitable Deagglomerationstosstoff represent the ethoxylated and alkoylated derivatives of 2-propylheptanols, which are sold under the trademarks Lutensol XL® and Lutensol XP® (BASF AG, DE).
- the deagglomerating assistant can be metered separately or added to the postcrosslinker solution.
- the deagglomerating aid is added to the postcrosslinker solution.
- the amount used of the deagglomerating assistant based on the base polymer is, for example, 0 to 0.01% by weight, preferably 0 to 0.005% by weight, particularly preferably 0 to 0.002% by weight.
- the deagglomerating aid becomes so metered in that the surface tension of an aqueous extract of the swollen base polymer and / or of the swollen postcrosslinked water-absorbing polymer at 23 ° C. is at least 0.060 N / m, preferably at least 0.062 N / m, particularly preferably at least 0.065 N / m, and advantageously at most 0.072 N / m.
- the dried base polymer used in the process according to the invention typically has a residual moisture content after drying and before application of the postcrosslinking solution from 0 to 13% by weight, preferably from 2 to 9% by weight.
- this moisture content can also be increased by up to 75% by weight, for example, by applying water in an upstream spray mixer.
- the moisture content is determined in accordance with the test method No. 430.2-02 "Moisture content" recommended by EDANA (European Disposables and Nonwovens Association). Such an increase in moisture content leads to a slight pre-swelling of the base polymer and improves the distribution of the crosslinker on the surface and the penetration of the particles.
- the spray nozzles which can be used in the process according to the invention are subject to no restriction.
- the liquid to be sprayed can be supplied under pressure.
- the division of the liquid to be sprayed can take place in that it is relaxed after reaching a certain minimum speed in the Düs senbohrung.
- single-substance nozzles such as, for example, slot nozzles or twist chambers (full-cone nozzles) can also be used for the purpose according to the invention (for example, by Düsen-Schlick GmbH, DE, or by Spraying Systems GmbH, DE).
- Such nozzles are also described in EP-A 534 228 and EP-A 1 191 051.
- the polymer powder is thermally dried, wherein the postcrosslinking reaction can take place before, during or after the drying.
- the spraying of the postcrosslinker solution is preferably carried out in mixers with moving mixing tools, such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers.
- moving mixing tools such as screw mixers, paddle mixers, disk mixers, plowshare mixers and paddle mixers.
- Vertical mixers are particularly preferred, plowshare mixers and paddle mixers are very particularly preferred.
- Suitable mixers are, for example, Lödige ⁇ mixers, BepexO mixers, Nauta® mixers, Processall® mixers and SchugiO mixers.
- the thermal drying is preferably carried out in contact dryers, particularly preferably paddle dryers, very particularly preferably disc dryers.
- Suitable dryers include Bepex® dryers and Nara® dryers.
- Math ⁇ this can also be used fluidized bed dryer.
- the drying can take place in the mixer itself, by heating the jacket or blowing hot air. Also suitable is a downstream dryer, such as a rack dryer, a rotary kiln or a heatable screw. It but can also be used as a drying process, for example, an azeotropic distillation.
- the postcrosslinker solution is particularly preferably applied to the base polymer in a high-speed mixer, for example of the Schugi-Flexomix® or Turbolizer® type, and thermally postcrosslinked in a reaction dryer, for example of the Nara- Paddle-Dryer® type or a disk dryer.
- the base polymer used may still have a temperature of 10 to 12O 0 C from previous process steps, the postcrosslinker solution may have a temperature of 0 to 150 0 C.
- postcrosslinker solution can be heated to reduce the viscosity.
- Preferred for postcrosslinking and drying the Tem ⁇ temperature range 30-220 0 C, in particular 150 to 210 0 C, particularly preferably 160 to 190 0 C.
- the preferred residence time at this temperature in the reaction mixer or dryer is below 100 minutes, more preferably less than 70 minutes, most preferably less than 40 minutes.
- the post-crosslinking dryer is purged with air during the drying and postcrosslinking reaction in order to remove the vapors.
- the dryer and the connected units are heated as completely as possible.
- the dried wasserabsorb Schl ⁇ the polymer particles are cooled.
- the warm and dry polymer is transferred to a downstream cooler in continuous operation.
- a downstream cooler in continuous operation.
- This may for example be a disc cooler, a Nara paddle cooler or a Schnecken ⁇ cooler. It is cooled over the walls and optionally the stirring elements of the radiator, which are flowed through by a suitable cooling medium such as warm or cold water.
- a suitable cooling medium such as warm or cold water.
- water or aqueous solutions of additives can be sprayed in the cooler; This increases the efficiency of the cooling (partial evaporation of water) and the residual moisture content in the finished product can be from 0 to 6% by weight, preferably from 0.01 to 4% by weight, more preferably from 0.1 to 3 % By weight.
- the increased residual moisture content reduces the dust content of the product.
- the water-absorbing polymer particles can be coated with water-insoluble metal phosphates, as described in WO 02/060983.
- the water-insoluble metal phosphates can be added as a powder or as a dispersion in a suitable dispersant, for example water.
- the water-insoluble metal phosphates are used and sprayed in the form of dispersions, they are preferably used as aqueous dispersions and it is preferred to additionally apply a dedusting agent for fixing the additive to the surface of the water-absorbing polymer.
- the dustproofing agent and the dispersion are preferably applied together with the postcrosslinking solution and, if appropriate, can be made from a common solution or from a plurality of separate solutions via separate nozzle systems in a time-equal or offset manner.
- Preferred dedusting agents are dendritic polymers, highly branched polymers, such as polyglycerols, polyethylene glycols, polypropylene glycols, random or block copolymers of ethylene oxide and propylene oxide.
- dedusting agents for this purpose are the polyethoxylates or polypropoxylates of polyhydroxy compounds, such as glycerol, sorbitol, trimethylolpropane, trimethylolethane and pentaerythritol.
- polyhydroxy compounds such as glycerol, sorbitol, trimethylolpropane, trimethylolethane and pentaerythritol.
- examples of these are n-times ethoxylated trimethylolpropane or glycerol, where n represents an integer between 1 and 100.
- block copolymers such as a total of n-times ethoxylated.es and then m-fold propoxylated trimethylolpropane or glycerol, wherein n represents an integer between 1 and 40 and m represents an integer between 1 and 40.
- the order of the blocks can also be reversed.
- the water-insoluble metal phosphates have an average particle size of usually less than 400 .mu.m, preferably less than 100 .mu.m, preferably less than 50 .mu.m, more preferably less than 10 .mu.m, most preferably the particle size range is from 2 to 7 .mu.m.
- water-insoluble metal phosphates only on the surface of the water-absorbing polymer particles.
- solutions of phosphoric acid or soluble phosphates and solutions of soluble metal salts are sprayed separately, with the water-insoluble metal phosphate forming and depositing on the particle surface.
- the coating with the water-insoluble metal phosphate can be carried out before, during or after the post-crosslinking step.
- the water-absorbing polymer particles B are preferably coated with water-insoluble metal phosphates.
- the water-absorbing polymer particles B have a higher content of polymer particles with a particle size of less than 300 .mu.m.
- the diesstechnikswei ⁇ tertechnisch (SFC) decreases with the particle size.
- SFC water-insoluble metal phosphates
- the fluid transfer (SFC) and the centrifuge retention capacity (CRC) influence each other, serunlös Anlagen metal phosphates and also with constant remplisstechniks shimmerer ⁇ line (SFC) the Zentrifugeretentionskapaztician (CRC) can be increased.
- coatings such as film-forming polymers, dendrimers, polycationic polymers (such as polyvinylamine, polyethyleneimine or polyallylamine), water-insoluble polyvalent metal salts such as calcium sulfate, water-soluble polyvalent metal salts such as aluminum sulfate, calcium or magnesium salts, or water-soluble zirconium salts, or hydrophilic inorganic particles, such as Tonminera ⁇ le, fumed silica, alumina and magnesium oxide, are additionally applied.
- additional effects for example a reduced tendency to bake, improved processing properties or a further increased liquid conductivity (SFC) can be achieved.
- the additives are used and sprayed on in the form of dispersions, they are preferably used as aqueous dispersions, and it is preferable to additionally apply a dedusting agent for fixing the additive to the surface of the water-absorbing polymer.
- water-absorbing polymer particles having good liquid transport properties and a good absorption effect are readily available.
- alkali metal silicates for the at least partial neutralization in the preparation of the base polymers.
- Post-treatment of the base polymer with polyvalent metal ions such as aluminum ions as aluminum sulfate solution, is likewise not necessary.
- solid powders in particular water-soluble polyvalent metal salts, for example aluminum salts, such as aluminum sulfate, potassium alum, aluminum nitrate, aluminum chloride or sodium alum, is unnecessary, in particular since the salt particles only act as spacers between the polymer particles and thus increase the fluid transfer in the short term they dissolve. Such spacers have no positive influence on the porosity and thus the wick absorption of wasser ⁇ absorbing polymer particles.
- aluminum salts such as aluminum sulfate, potassium alum, aluminum nitrate, aluminum chloride or sodium alum
- hydrophilic inorganic particles for example clay minerals and pyrogenic silica, alumina and magnesium oxide, likewise only leads to an increased liquid transfer (SFC) without improving wick absorption.
- the polymers of the invention are characterized by a high wick absorption. This can be determined by the wick absorption test described below become. It is expressed by a high initial absorption and high liquid absorption after 60 and 240 minutes. In addition, particularly good superabsorbent polymers are distinguished by the fact that even after more than 150 minutes further liquid absorption takes place.
- the amount is 0.9% strength by weight sodium chloride solution which absorbs the polymers according to the invention within 60 minutes, preferably at least 250 g, more preferably at least 300 g, and the amount 0.9% by weight. iger saline, which absorb the polymers of the invention within 240 minutes, preferably at least 300 g, more preferably min ⁇ least 350 g.
- the amount of 0.9% by weight saline solution which absorbs the polymers according to the invention within 60 minutes is preferably at least 100 g, in particular preferably at least 150 g, and the amount of 0.9 wt .-% sodium chloride solution, which absorb the polymers of the invention within 240 minutes vorzugswei ⁇ se at least 115 g, more preferably at least 125 g.
- the amount is 0.9% by weight saline solution which absorbs the polymers according to the invention within 60 minutes, preferably at least 50 g, preferably at least 60 g, more preferably at least 70 g.
- the polymers of the invention are further characterized in that the wick absorption and the liquid conductivity are both optimized so that the product of these two parameters is optimized for liquid transport.
- This fluid transfer product (SFC) and wick absorption after 60 min (DA 6 o) multiplied by 10 7 is referred to as transport value (TW) and calculated according to the formula given below.
- Centrifuge retention capacity (CRC) and fluid transfer (SFC) are optimized via the degree of neutralization of the base polymer as well as centrifuge retention capacity (CRC) and transport value (TW) via the reaction conditions in the post-crosslinking.
- low postcrosslinked polymer particles generally have a high centrifuge retention capacity (CRC) and a low transport value (TW)
- highly postcrosslinked polymer particles generally have a low centrifuge retention capacity (CRC) and a high transport value (TW), the extent of postcrosslinking also being greater than the reaction temperature and the reaction time is determined.
- the water-absorbing polymer particles according to the invention are largely free of compounds which, especially during use, lead to unpleasant odors.
- the water-absorbing polymer particles according to the invention are very white, which is necessary in particular in ultrathin diapers with a high proportion of ementabsorb Schl ⁇ the polymer particles. Ultra-thin diapers show little color variation through the thin top layer, which customers do not accept.
- a further subject of the present invention are hygiene articles comprising water-absorbing polymer particles according to the invention, preferably ultrathin diapers, containing an absorbent layer consisting of 50 to 100 wt.%, Preferably 60 to 100 wt.%, Preferably 70 to 100 wt. particularly preferably from 80 to 100% by weight, very particularly preferably from 90 to 100% by weight, of water-absorbing polymer particles according to the invention, wherein the coating of the absorbent layer is of course not taken into account.
- the water-absorbing polymer particles according to the invention are also particularly advantageously also suitable for the production of laminates and composite structures, as described, for example, in US-A 2003/0181115 and US-A 2004/0019342.
- the water-absorbing polymer particles according to the invention are also suitable for Production of completely ana ⁇ logen structures using UV-crosslinkable hotmelt adhesives, which are sold for example as AC Resin® (BASF AG, DE).
- UV-crosslinkable hot-melt adhesives have the advantage of being processable at as low as 120 to 140 ° C., so they are more compatible with many thermoplastic substrates. Another significant advantage is that UV-crosslinkable hotmelt adhesives are toxicologically very harmless and also cause no exhalations in the hygiene articles.
- a very significant advantage, in connection with the water-absorbing polymer particles according to the invention, is that the property of the UV-crosslinkable hot-melt adhesive during processing and crosslinking is not prone to yellowing. This is particularly advantageous if ultrathin or partially transparent hygiene articles are to be produced. The combination of the water-absorbing polymer particles according to the invention with UV-crosslinkable hotmelt adhesives is therefore particularly advantageous. Suitable UV-crosslinkable hotmelt adhesives are described, for example, in EP-A 377 199, EP-A 445 641, US Pat. No. 5,026,806, EP-A 655 465 and EP-A 377 191.
- the dried water-absorbing polymer particles are tested by the test methods described below.
- centrifuge retention capacity is determined according to the test method No. 441.2-02 "Centrifugal Retention Capacity" recommended by the EDANA (European Dispo- sables and Nonwovens Association), but deviating from this for each example the actual sample is measured with the particle size distribution given there.
- the absorption under pressure is determined in accordance with the test method No. 442.2-02 "Absorption under pressure" recommended by the EDANA (European Disposables and Nonwovens Association), but deviating from this for each example the actual sample with the particle size distribution indicated there is measured.
- Fluid transfer is calculated as follows:
- LO is the thickness of the gel layer in cm
- d the density of the NaCl solution in g / cm 3
- A is the area of the gel layer in cm 2
- WP is the hydrostatic pressure over the gel layer in dynes / cm 2 .
- the content of extractable constituents of the water-absorbing polymer particles is determined according to the test method No. 470.2-02 "Determination of extractable polymer content by potentiometry titration" recommended by EDANA (European Disposables and Nonwovens Association).
- the pH of the water-absorbing polymer particles is determined according to the test method No. 400.2-02 "Determination of pH” recommended by the E-DANA (European Disposables and Nonwovens Association).
- the weight W1 should be corrected by this moisture content.
- the water content of the water-absorbing polymer particles is determined according to the test method No. 430.2-02 "Moisture content" recommended by the EDANA (European Disposables and Nonwovens Association). wicking absorption
- FIG. 1a Construction of the apparatus as shown in FIG. 1a (side view) and FIG. 1b (top view):
- a cylindrical 1,000 ml dropping funnel (DIN 12566 graduated, with conical grinding sleeve NS 29/32, cock with hollow glass chicks and drainage tube made of Duranglas, graduation: 20 ml, height 39.5 cm, manufacturer: Heico) with two-neck attachment made of Duranglas, Conical loops NS 19/26 and NS 29/32 (height 11 cm) are filled with 1,000 ml of 0.9% saline solution. Then a glass tube (length 47 cm, inner diameter: 1, 5 mm, personally ⁇ diameter: 4 mm) is inserted as deep as possible in the dropping funnel. The glass tube is closed with a pierced rubber stopper (or a screw seal) on the one opening of the two-neck attachment against the outside atmosphere.
- a pierced rubber stopper or a screw seal
- a scale connected to a computer is set. Then a Plexiglas plate (area: 12 x 12 cm 2 , height: 1.5 cm), which is welded to a Plexiglas cylinder (height: 13.5 cm), is placed on the balance.
- a P 0 glass frit with a diameter of 7 cm and a height of 0.45 cm is embedded liquid-tight, ie the liquid exits through the pores of the frit and not over the edge between Plexiglas plate and frit.
- a Plexiglas pipe with curvature in the middle of the Plexiglas cylinder is attached to ensure the liquid transport. This tube has the same diameter as the outlet of the dropping funnel.
- the liquid tube is now connected to the dropping funnel with a flexible hose (length 37 cm, outer diameter 1, 0 cm, inner diameter 0.7 cm) in such a way that no pressure is exerted on the balance by the connection.
- the upper side of the frit is now brought to the level of the lower En ⁇ of the glass tube, so that during the measurement, a steadily pressureless (At ⁇ atmospheric pressure) liquid flow is ensured from the dropping funnel to the measuring apparatus.
- the top of the frit is adjusted so that its surface is moist, but no water film is on the frit. (If this is the case, the frit is adjusted incorrectly.)
- no continuous film of liquid may form on the frit even after 5 minutes have passed the weight of the scale must remain unchanged during this time If gas bubbles should be visible on the underside of the frit, these are removed, for example, by using an extraction system.
- the tap of the dropping funnel is open; as soon as the adjustment is completed, it is closed. Proper functioning is checked before each attempt. Before each experiment, the liquid in the dropping funnel is made up to 1,000 ml.
- the tap of the dropping funnel is opened and the electronic data logging is started.
- the increase in weight on the scale is recorded as a function of time. This then indicates how much salt solution has been taken up at a certain time by the swelling gel column of the water-absorbing polymer particles.
- the gel column is allowed to swell for 60 or 240 minutes.
- the data are recorded automatically every 10 seconds.
- the test can be carried out without pressure, meaning that there is no weight on the gel column during the swelling process.
- AUL under absorption under pressure
- Typical weight loads are 0.3 psi (2.07 kPa) and 0.7 psi (4.83 kPa).
- the measurement is preferably carried out without pressure and at 0.3 psi and 0.7 psi for a period of 60 or 240 minutes per sample.
- the absorption data relate in each case to the total amount of saline solution absorbed by the 70 g sample.
- DA nn The total amount of saline solution (in grams) taken up by the 70 g sample within a certain time is referred to as wick absorption and denoted as follows: DA nn , where the subscript nn denotes the absorption time in minutes, for example DA 60 means the unpressurized one Absorption after 60 minutes. If a pressure acts during the swelling process, then this is shown in parentheses, for example, DA 24 o (0.3 psi) means the absorption under a pressure of 0.3 psi after 240 minutes. Transport value (TW)
- the wick absorption and liquid conductivity (SFC) product characterizes the ability of the water-absorbing polymer particles to transport liquids when swelling or through the swollen gel layer.
- This product of SFC and DA 6O (non-pressurized wick absorption after 60 min) is called transport value (TW) and calculated as follows:
- TW [cm 3 s] SFC [cm 3 s / g] x DA 60 [g] x 10 7
- the values for a * and b * indicate the position of the color on the red / green and yellow / blue color axes, where + a * is red, -a * is green, + b * is yellow, and -b * is blue stands.
- the color measurement corresponds to the tristimulus method according to DIN 5033-6.
- the Hunter 60 value is a measure of the whiteness of surfaces and is defined as L * -3b *, that is, the lower the value, the darker and the more yellowish one color.
- the EDANA test methods are available, for example, from the European Dispensables and Nonwovens Association, Avenue Eugene Plasky 157, B-1030 Brussels, Associates. Examples
- the dried base polymer was ground and sieved to 300 to 600 ⁇ m.
- the properties of the polymer were as follows:
- the postcrosslinking solution had the following composition: 0.02 g of 2-oxazolidone, 0.01 g of sorbitan monococoate, 0.97 g of water.
- the moistened polymer was homogenized by stirring and then tempered on a watch glass in a convection oven for 90 minutes at 175 ° C. Finally, it was sieved through a 600 ⁇ m sieve to remove lumps.
- the polymer had the following properties:
- the postcrosslinking solution had the following composition: 0.020 g of N-hydroxyethyl-2-oxazolidone, 0.005 g of sorbitan monococoate, 0.975 g of water.
- the moistened polymer was homogenized by stirring and then tempered on a watch glass in a convection oven for 90 minutes at 175 ° C. Finally, it was sieved through a 600 ⁇ m sieve to remove lumps.
- the polymer had the following properties:
- the postcrosslinking solution had the following composition: 0.020 g of 2-oxazolidone, 0.020 g of 1,2-propanediol, 0.010 g of sorbitan monococoate, 0.95 g of water.
- the moistened polymer was homogenized by stirring and then tempered on a watch glass in a convection oven for 90 minutes at 175 ° C. Finally, it was sieved through a 600 ⁇ m sieve to remove lumps.
- the polymer had the following properties:
- the postcrosslinking solution had the following composition: 0.020 g of 2-oxazolidone, 0.29 g of isopropanol, 0.69 g of water.
- the moistened polymer was homogenized by stirring and then tempered on a watch glass in a convection oven for 90 minutes at 175 ° C. Finally, it was sieved through a 600 ⁇ m sieve to remove lumps.
- the polymer had the following properties:
- Example 2 Analogously to Example 1, in a Lödige ploughshare kneader type VT 5R-MK (5 l volume) at a solids content of 35.5% by weight and degrees of neutralization of 60 mol%, 65 mol%, 70 mol%, 75 mol%, and 85 mol% and a crosslinker use of 0.70 wt .-% polyethylene glycol-400-diacrylate (based on acrylic acid) wasserabsor ⁇ bierende polymers produced.
- the initiation was carried out analogously to Example 1 after presentation of the starting materials. They were inertized for 20 minutes while sparging with nitrogen.
- the dried base polymer was ground and sieved to 200 to 850 microns.
- composition of the postcrosslinking solution is defined so that, based on the base polymer used, 3.43% by weight of water, 1.47% by weight of isopropanol, and 0.10% by weight of oxazolidone were applied.
- the moistened polymer was homogenized by stirring and then the polymers were tempered on watch glasses in convection oven cabinets for 60 minutes at 175 ° C. Finally, it was sieved through a 850 ⁇ m sieve to remove lumps.
- the preparation example of the base polymer of Example 1 was repeated.
- the dried base polymer was ground and sieved to 300 to 600 ⁇ m.
- the properties of the base polymer (300 to 600 ⁇ m) were as follows:
- the post-crosslinking was carried out completely analogously to Examples 2a to 2d.
- the following table gives the amounts of starting material in wt .-% based on the base polymer used and the reaction conditions.
- Postcrosslinker 1 and, if appropriate, postcrosslinker 2 were dissolved together with 0.02% by weight of sorbitan monococoate (deagglomerating agent, Emulsogen V 4345 from Clariant, DE), based on the polymer employed, and, if appropriate, the cosolvent and dissolved in the Waring blender the base polymer is sprayed on. Subsequently, on a watch glass in a circulating air oven dried at the specified residence time and reaction temperature. The results are summarized in Table 2.
- the base polymer preparation example of Example 1 was repeated.
- the dried base polymer was ground and sieved to 300 to 600 ⁇ m.
- the properties of the base polymer (300 to 600 ⁇ m) were as follows:
- the post-crosslinking was carried out completely analogously to Examples 2a to 2d.
- the following table gives the amounts of starting material of the crosslinker mixed with water in wt .-% based on the base polymer used.
- 20 g base polymer from Example 15 were sprayed in the Waring Blender with the specified mixture which still contained 0.02% by weight sorbitan monococoate (deagglomerating agent Emulsogen V 4345, CI riant, DE), based on the polymer used and mixed. It was then dried on a watch glass in a circulating air oven at 175 ° C for 60 minutes.
- Tables 3 and 4 The results are summarized in Tables 3 and 4.
- Examples 19 to 22 and 25 to 27 are examples of low-reactive Nachvernet- zer, which are preferably used as cosolvent.
- the post-crosslinking was carried out completely analogously to Examples 2a to 2d.
- the following table gives the amounts of starting material of the crosslinker mixed with water in wt .-% based on the base polymer used.
- Tables 5 and 6 The results are summarized in Tables 5 and 6.
- Examples 37, 38, 40 and 41 less reactive postcrosslinkers were used as co-solvents, which form strong-smelling by-products which make it difficult to use water-absorbing polymer particles prepared in hygiene articles. Furthermore, the diols of Examples 37 and 38 tend to form a slight yellowing, evidenced by the slightly increased b-color index value.
- Example 39 Although the water-absorbing polymer particles from Example 39 contain no unpleasant-smelling compounds, a cyclic by-product (tetrahydrofuran) has formed here, which is likewise undesirable in hygiene articles.
- Examples 42 to 57 preferred less reactive postcrosslinkers were used as co-sovereigns for reactive crosslinkers, in this case 2-oxazolidone. These mixtures lead to virtually odorless and white products.
- the polymer powder obtained had the following properties:
- This base polymer was prepared completely analogously to Example 58, only the sieving was changed accordingly so that a lower fines content was produced in the product.
- Extractable 16h 13% by weight
- Residual monomer acrylic acid 240 ppm
- This base polymer was prepared completely analogously to Example 58, only the screening was changed accordingly so that only a small amount of coarse fraction remained in the product.
- Extractable 16h 12.9 wt%
- Residual monomer acrylic acid 230 ppm
- Examples 61 to 66 In a Lödige ploughshare kneader type VT 5R-MK (5 l volume), 1.2 kg of base polymer from Example 60 were initially introduced. Then, using the solvent mixture isopropanol / water in the tabulated amounts below, the respective crosslinker mixture dissolved in this solvent was sprayed by means of a two-component nozzle with stirring. All quantities in the table are wt .-%, based on the submitted base polymer. If appropriate, an additive was also applied which was previously dispersed or dissolved in the postcrosslinking solution. After spraying, the reactor jacket was heated with heating fluid while stirring, with a rapid heating rate being advantageous for the product properties.
- SEA (C13-09) calcium phosphate type C13-09, Fa. Budenheim
- EDGE ethylene glycol diglycidyl ether (Denacol EX 810, Nagase)
- Examples 67 to 72 show that by the method according to the invention high values for the centrifuge retention capacity (CRC) and the liquid transfer (SFC) are compatible with a very high proportion of particles ⁇ 300 ⁇ m (25% by weight) in the Aus ⁇ material and in the final product.
- CRC centrifuge retention capacity
- SFC liquid transfer
- Examples 73 to 78 show that according to the process of the invention the centrifuge retention capacity (CRC) can be increased even further without impairing the liquid transfer (SFC) if the proportion of particles ⁇ 300 ⁇ m in the starting material and in the end product below 15% by weight. % reduced.
- CRC centrifuge retention capacity
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- Absorbent Articles And Supports Therefor (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
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Priority Applications (4)
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US11/665,883 US7759422B2 (en) | 2004-10-20 | 2005-10-14 | Fine-grained water-absorbent particles with a high fluid transport and absorption capacity |
JP2007537171A JP2008517116A (ja) | 2004-10-20 | 2005-10-14 | 高い液体輸送性および吸水性能を有する微粒子状の吸水性ポリマー粒子 |
EP05798199A EP1804842A2 (de) | 2004-10-20 | 2005-10-14 | Feinteilige wasserabsorbierende polymerpartikel mit hoher flüssigkeitstransport- und absorptionsleistung |
CN200580043376XA CN101080245B (zh) | 2004-10-20 | 2005-10-14 | 具有高流体输送和吸收能力的细粒状吸水性聚合物颗粒 |
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DE102004051242A DE102004051242A1 (de) | 2004-10-20 | 2004-10-20 | Feinteilige wasserabsorbierende Polymerpartikel mit hoher Flüssigkeitstransport- und Absorptionsleistung |
DE102004051242.6 | 2004-10-20 |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002060983A2 (de) * | 2001-01-19 | 2002-08-08 | Basf Aktiengesellschaft | Wasserabsorbierendes mittel, verfahren zu seiner herstellung und seine verwendung |
WO2004024816A1 (de) * | 2002-08-26 | 2004-03-25 | Basf Aktiengesellschaft | Wasserabsorbierendes mittel und verfahren zu seiner herstellung |
WO2004052949A1 (de) * | 2002-12-09 | 2004-06-24 | Basf Aktiengesellschaft | Verfahren zur herstellung geruchsarmer hydrogel-bildender polymerisate |
WO2005080479A1 (de) * | 2004-02-24 | 2005-09-01 | Basf Aktiengesellschaft | Verfahren zur nachvernetzung wasserabsorbierender polymere |
WO2005097881A1 (de) * | 2004-03-29 | 2005-10-20 | Basf Aktiengesellschaft | Quellbare hydrogelbildende polymere mit hoher permeabilität |
WO2006015729A2 (de) * | 2004-08-04 | 2006-02-16 | Basf Aktiengesellschaft | Verfahren zur nachvernetzung wasserabsorbierender polymere mit zyklischen carbamaten und/oder zyklischen harnstoffen |
Family Cites Families (59)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6018690B2 (ja) | 1981-12-30 | 1985-05-11 | 住友精化株式会社 | 吸水性樹脂の吸水性改良方法 |
JPS58180233A (ja) | 1982-04-19 | 1983-10-21 | Nippon Shokubai Kagaku Kogyo Co Ltd | 吸収剤 |
US4734478A (en) | 1984-07-02 | 1988-03-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Water absorbing agent |
DE3817425A1 (de) | 1988-05-21 | 1989-11-23 | Cassella Ag | Alkenyl-phosphon- und -phosphin-saeureester, verfahren zu ihrer herstellung sowie unter deren verwendung hergestellte hydrogele und deren verwendung |
DE3836968A1 (de) | 1988-10-31 | 1990-05-03 | Basf Ag | Uv-vernetzbare massen auf basis von isoamyl(meth)acrylatcopolymerisaten |
DE3844444A1 (de) | 1988-12-31 | 1990-08-09 | Basf Ag | Strahlungsempfindliche, ethylenisch ungesaettigte, copolymerisierbare verbindungen und verfahren zu deren herstellung |
DE3844445A1 (de) | 1988-12-31 | 1990-07-19 | Basf Ag | Uv-vernetzbare massen auf basis von (meth)-acrylesterpolymerisaten |
WO1990015830A1 (en) | 1989-06-12 | 1990-12-27 | Weyerhaeuser Company | Hydrocolloid polymer |
DE4007318A1 (de) | 1990-03-08 | 1991-09-12 | Basf Ag | Ethylenisch ungesaettigte verbindungen |
CA2038779A1 (en) | 1990-04-02 | 1991-10-03 | Takumi Hatsuda | Method for production of fluid stable aggregate |
DE4020780C1 (de) | 1990-06-29 | 1991-08-29 | Chemische Fabrik Stockhausen Gmbh, 4150 Krefeld, De | |
DK0530438T3 (da) | 1991-09-03 | 1997-08-18 | Hoechst Celanese Corp | Superabsorberende polymer med forbedrede absorptionsegenskaber |
DE4131045C1 (de) | 1991-09-18 | 1992-11-19 | Cassella Ag, 6000 Frankfurt, De | |
DE4138408A1 (de) | 1991-11-22 | 1993-05-27 | Cassella Ag | Hydrophile, hochquellfaehige hydrogele |
JP3045422B2 (ja) | 1991-12-18 | 2000-05-29 | 株式会社日本触媒 | 吸水性樹脂の製造方法 |
EP0559476B1 (de) | 1992-03-05 | 1997-07-16 | Nippon Shokubai Co., Ltd. | Verfahren zu Herstellung eines absorbierenden Harzes |
GB9208449D0 (en) | 1992-04-16 | 1992-06-03 | Dow Deutschland Inc | Crosslinked hydrophilic resins and method of preparation |
US5574121A (en) | 1993-06-18 | 1996-11-12 | Nippon Shokubai Co., Ltd. | Process for preparing an absorbent resin crosslinked with a mixture of trimethylolpropane diacrylate and triacrylate |
NZ268535A (en) | 1993-06-30 | 1998-05-27 | Procter & Gamble | Absorbent article comprising layers of superabsorbent material |
JP3722858B2 (ja) | 1993-11-25 | 2005-11-30 | ビーエーエスエフ アクチェンゲゼルシャフト | ポリアクリレート溶融体から残留揮発分を除去する方法 |
US5599335A (en) | 1994-03-29 | 1997-02-04 | The Procter & Gamble Company | Absorbent members for body fluids having good wet integrity and relatively high concentrations of hydrogel-forming absorbent polymer |
US5624967A (en) | 1994-06-08 | 1997-04-29 | Nippon Shokubai Co., Ltd. | Water-absorbing resin and process for producing same |
DE19543368C2 (de) | 1995-11-21 | 1998-11-26 | Stockhausen Chem Fab Gmbh | Wasserabsorbierende Polymere mit verbesserten Eigenschaften, Verfahren zu deren Herstellung und deren Verwendung |
DE19646484C2 (de) | 1995-11-21 | 2000-10-19 | Stockhausen Chem Fab Gmbh | Flüssigkeitsabsorbierende Polymere, Verfahren zu deren Herstellung und deren Verwendung |
DE19807502B4 (de) * | 1998-02-21 | 2004-04-08 | Basf Ag | Verfahren zur Nachvernetzung von Hydrogelen mit 2-Oxazolidinonen, daraus hergestellte Hydrogele und deren Verwendung |
US6265488B1 (en) | 1998-02-24 | 2001-07-24 | Nippon Shokubai Co., Ltd. | Production process for water-absorbing agent |
US6503979B1 (en) | 1998-02-26 | 2003-01-07 | Basf Aktiengesellschaft | Method for cross-linking hydrogels with bis- and poly-2-oxazolidinones |
KR100476170B1 (ko) | 1998-04-28 | 2005-03-10 | 니폰 쇼쿠바이 컴파니 리미티드 | 흡수성수지 함수겔상물의 제조방법 |
DE19854573A1 (de) | 1998-11-26 | 2000-05-31 | Basf Ag | Verfahren zur Nachvernetzung von Hydrogelen mit 2-Oxo-tetrahydro-1,3-oxazinen |
DE19854574A1 (de) | 1998-11-26 | 2000-05-31 | Basf Ag | Verfahren zur Nachvernetzung von Hydrogelen mit N-Acyl-2-Oxazolidinonen |
DE19909653A1 (de) * | 1999-03-05 | 2000-09-07 | Stockhausen Chem Fab Gmbh | Pulverförmige, vernetzte, wässrige Flüssigkeiten sowie Blut absorbierende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19909838A1 (de) * | 1999-03-05 | 2000-09-07 | Stockhausen Chem Fab Gmbh | Pulverförmige, vernetzte, wässrige Flüssigkeiten sowie Blut absorbierende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19941423A1 (de) | 1999-08-30 | 2001-03-01 | Stockhausen Chem Fab Gmbh | Polymerzusammensetzung und ein Verfahren zu dessen Herstellung |
US6239230B1 (en) | 1999-09-07 | 2001-05-29 | Bask Aktiengesellschaft | Surface-treated superabsorbent polymer particles |
DE19955861A1 (de) | 1999-11-20 | 2001-05-23 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von vernetzten feinteiligen gelförmigen Polymerisaten |
JP2003518150A (ja) | 1999-12-23 | 2003-06-03 | ザ ダウ ケミカル カンパニー | 高透過性で低吸収容量のポリマー |
US6720389B2 (en) | 2000-09-20 | 2004-04-13 | Nippon Shokubai Co., Ltd. | Water-absorbent resin and production process therefor |
WO2002032962A2 (en) | 2000-10-20 | 2002-04-25 | Millennium Pharmaceuticals, Inc. | Compositions of human proteins and method of use thereof |
US6809158B2 (en) | 2000-10-20 | 2004-10-26 | Nippon Shokubai Co., Ltd. | Water-absorbing agent and process for producing the same |
WO2002053199A1 (de) * | 2000-12-29 | 2002-07-11 | Basf Aktiengesellschaft | Hydrogele mit sterischen oder elektrostatischen abstandhaltern beschichtet |
US6766807B2 (en) * | 2001-03-05 | 2004-07-27 | Snow Ellen Piccolo | Combination floss dispenser and toothbrush |
US6766817B2 (en) | 2001-07-25 | 2004-07-27 | Tubarc Technologies, Llc | Fluid conduction utilizing a reversible unsaturated siphon with tubarc porosity action |
US8426670B2 (en) | 2001-09-19 | 2013-04-23 | Nippon Shokubai Co., Ltd. | Absorbent structure, absorbent article, water-absorbent resin, and its production process and evaluation method |
US7183360B2 (en) | 2001-10-05 | 2007-02-27 | Basf Aktiengesellschaft | Method for crosslinking hydrogels with morpholine-2,3-diones |
PL363038A1 (en) | 2002-02-04 | 2004-11-15 | Nippon Shokubai Co, Ltd. | Absorptive material, method for producing the same and absorptive article using the same |
DE10204938A1 (de) | 2002-02-07 | 2003-08-21 | Stockhausen Chem Fab Gmbh | Verfahren zur Nachvernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren mit beta-Hydroxyalkylamiden |
DE10204937A1 (de) | 2002-02-07 | 2003-08-21 | Stockhausen Chem Fab Gmbh | Verfahren zur Nachvernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren mit Harnstoffderivaten |
DE10225943A1 (de) | 2002-06-11 | 2004-01-08 | Basf Ag | Verfahren zur Herstellung von Estern von Polyalkoholen |
AU2003238476A1 (en) | 2002-06-11 | 2003-12-22 | Basf Aktiengesellschaft | (meth)acrylic esters of polyalkoxylated trimethylolpropane |
ES2263988T3 (es) | 2002-06-11 | 2006-12-16 | Basf Aktiengesellschaft | Esteres de (met)acrilato de glicerina polialcoxilada. |
PL215419B1 (pl) | 2003-02-10 | 2013-12-31 | Nippon Catalytic Chem Ind | Srodek pochlaniajacy wode |
JP4739682B2 (ja) * | 2003-02-10 | 2011-08-03 | 株式会社日本触媒 | 吸水剤 |
EP1594608B1 (de) | 2003-02-10 | 2013-07-17 | Nippon Shokubai Co., Ltd. | Teilchenförmiges wasserabsorptionsmittel, das als hauptkomponente wasserabsorbierendes harz enthält |
US8247491B2 (en) | 2003-02-10 | 2012-08-21 | Nippon Shokubai Co., Ltd. | Water-absorbent resin composition and its production process |
DE10331456A1 (de) | 2003-07-10 | 2005-02-24 | Basf Ag | (Meth)acrylsäureester alkoxilierter ungesättigter Polyolether und deren Herstellung |
DE10331450A1 (de) | 2003-07-10 | 2005-01-27 | Basf Ag | (Meth)acrylsäureester monoalkoxilierter Polyole und deren Herstellung |
DE10334584A1 (de) | 2003-07-28 | 2005-02-24 | Basf Ag | Verfahren zur Nachvernetzung von Hydrogelen mit bicyclischen Amidacetalen |
JP4695370B2 (ja) * | 2003-09-19 | 2011-06-08 | 株式会社日本触媒 | 表面処理された吸水性樹脂の製造方法 |
DE10355401A1 (de) | 2003-11-25 | 2005-06-30 | Basf Ag | (Meth)acrylsäureester ungesättigter Aminoalkohole und deren Herstellung |
-
2004
- 2004-10-20 DE DE102004051242A patent/DE102004051242A1/de not_active Withdrawn
-
2005
- 2005-10-14 EP EP10173417A patent/EP2263704A1/de not_active Withdrawn
- 2005-10-14 WO PCT/EP2005/011073 patent/WO2006042704A2/de active Application Filing
- 2005-10-14 CN CN200580043376XA patent/CN101080245B/zh active Active
- 2005-10-14 US US11/665,883 patent/US7759422B2/en active Active
- 2005-10-14 JP JP2007537171A patent/JP2008517116A/ja active Pending
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002060983A2 (de) * | 2001-01-19 | 2002-08-08 | Basf Aktiengesellschaft | Wasserabsorbierendes mittel, verfahren zu seiner herstellung und seine verwendung |
WO2004024816A1 (de) * | 2002-08-26 | 2004-03-25 | Basf Aktiengesellschaft | Wasserabsorbierendes mittel und verfahren zu seiner herstellung |
WO2004052949A1 (de) * | 2002-12-09 | 2004-06-24 | Basf Aktiengesellschaft | Verfahren zur herstellung geruchsarmer hydrogel-bildender polymerisate |
WO2005080479A1 (de) * | 2004-02-24 | 2005-09-01 | Basf Aktiengesellschaft | Verfahren zur nachvernetzung wasserabsorbierender polymere |
WO2005097881A1 (de) * | 2004-03-29 | 2005-10-20 | Basf Aktiengesellschaft | Quellbare hydrogelbildende polymere mit hoher permeabilität |
WO2006015729A2 (de) * | 2004-08-04 | 2006-02-16 | Basf Aktiengesellschaft | Verfahren zur nachvernetzung wasserabsorbierender polymere mit zyklischen carbamaten und/oder zyklischen harnstoffen |
Non-Patent Citations (1)
Title |
---|
See also references of EP1804842A2 * |
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Also Published As
Publication number | Publication date |
---|---|
CN101080245B (zh) | 2012-06-06 |
WO2006042704A3 (de) | 2006-08-10 |
EP2263704A1 (de) | 2010-12-22 |
CN101080245A (zh) | 2007-11-28 |
US7759422B2 (en) | 2010-07-20 |
EP1804842A2 (de) | 2007-07-11 |
US20080125533A1 (en) | 2008-05-29 |
JP2008517116A (ja) | 2008-05-22 |
EP2258409A1 (de) | 2010-12-08 |
DE102004051242A1 (de) | 2006-05-04 |
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