US20040180189A1 - Acidic superabsorbent hydrogels - Google Patents

Acidic superabsorbent hydrogels Download PDF

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Publication number
US20040180189A1
US20040180189A1 US10/480,980 US48098003A US2004180189A1 US 20040180189 A1 US20040180189 A1 US 20040180189A1 US 48098003 A US48098003 A US 48098003A US 2004180189 A1 US2004180189 A1 US 2004180189A1
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Prior art keywords
weight
acrylic acid
weight based
hydrogel forming
acid
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Abandoned
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US10/480,980
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Inventor
Rudiger Funk
Norbert Herfert
Mariola Wanior
Uwe Stuven
Martin Beck
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BASF SE
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Assigned to BASF AKTIENGESELLSCHAFT, A GERMAN CORPORATION reassignment BASF AKTIENGESELLSCHAFT, A GERMAN CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BECK, MARTIN, FUNK, RUDIGER, HERFERT, NORBERT, STUVEN, UWE, WANIOR, MARIOLA
Publication of US20040180189A1 publication Critical patent/US20040180189A1/en
Priority to US11/145,653 priority Critical patent/US20050234413A1/en
Priority to US11/706,906 priority patent/US7915363B2/en
Priority to US11/872,815 priority patent/US7790823B2/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/10—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • Zeolites, active carbon, bentonites, finely divided amorphous silicas such as AEROSIL® or CAB-O-SIL® are used here.
  • cyclodextrins any modification of unsubstituted cyclodextrins which contains from 6 to 12 glucose units, for example alpha-cyclodextrin and beta-cyclodextrin, gamma-cyclodextrin and/or derivatives and/or mixtures thereof. Mixtures of cyclodextrins are preferred, since they provide broader complexation of organic molecules over a wider molecular weight range. Cyclodextrins are used from 0.1% to about 25%, preferably from 1% to about 20%, more preferably from 2% to about 15% and especially from 3 to 10%, based on the total weight of the composition.
  • Cyclodextrins are added in small particle size (usually less than 12 ⁇ m) to offer a large surface area for odor elimination.
  • Further complexing agents are aminopolycarboxylic acids and their salts, ethylenediaminetetraacetate EDTA ethylenediaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, aminophosphates, polyfunctional aromatics, N,N-disuccinic acid.
  • Nonlimiting examples of perfumes are allyl caproate, allylcyclohexane acetate, allylcyclohexane propionate, allyl heptanoate, amyl acetate, amyl propionate, anetole, anisole, benzaldehyde, benzyl acetate, benzylacetone, benzyl alcohol, benzyl butyrate, benzyl formate, benzyl isovalerate, benzyl propionate, butyl benzoate, butyl caproate, camphor, cis-3-hexenyl acetate, cis-3-hexenyl butyrate, cis-3-hexenyl caproate, cis-3-hexenyl valerate, citronellol, citronellyl derivates, Cyclal C, cyclohexylethyl acetate, 2-decenal, decylalde
  • EP 0 583 178 B1 proposes a process for preparing superabsorbent powders consisting of partially neutralized polyacrylic acids by a sequential inverse suspension polymerization of two charges having different degrees of neutralization (Charge I: degree of neutralization 90-100%, Charge III: degree of neutralization 50-60%), charge II being absorbed before polymerization by the polymer of charge I.
  • the invention accordingly provides a process for screening superabsorbents which comprises determining or estimating the pH, CRC and AUL 0.7 psi of a plurality of absorbent samples and determining or estimating the pH absorbency index therefrom. Repeated (iterative) application of this screening process by varying one or more opposing or nonopposing parameters makes it possible to optimize the superabsorbent through varied production processes from each measurement of the pH absorbency index.
  • the novel superabsorbents optimized by this process are likewise claimed.
  • a method for determining the swellability of polymer gels under pressure is described in PCT/EP/01/12959 and can be appropriately adapted. The disclosure content of this PCT specification is incorporated in the disclosure content of the present invention.
  • Acidic hydrogel material according to the invention in contrast, comprises complete odor control due to effective control of bacterial growth and high absorption performance coupled with a summation factor of above 100, for example in the range from 100 to 130.
  • n is an integer from 1 to 10 000.
  • dialkylaminoethyl acrylate and dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate are also possible.
  • the basic esters are preferably used in quaternized form or as salt. It is also possible to use glycidyl (meth)acrylate, for example.
  • the crosslinkers are present in the reaction mixture for example from 0.001 to 20% and preferably from 0.01 to 14% by weight.
  • the initiator used is customarily a photoinitiator.
  • Photoinitiators include for example ⁇ -splitters, H-abstracting systems or else azides.
  • examples of such initiators are benzophenone derivatives such as Michler's ketone, phenanthrene derivatives, fluorene derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, benzoin ethers and derivatives thereof, azo compounds such as the abovementioned free-radical formers, substituted hexaarylbisimidazoles or acylphosphine oxides.
  • the polymerization reaction may be carried out at from 0 to 150° C., preferably at from 10 to 100° C., not only at atmospheric pressure but also at superatmospheric or reduced pressure.
  • the polymerization may also be conducted in a protective gas atmosphere, preferably under nitrogen.
  • the following list relates to particularly preferred conditions for production processes of gels and of dried gels prior to surface postcrosslinking (base polymers). The missing weight percent from 100% are to be made up with water.
  • NaOH 50% 22-30 mol % based on acrylic acid, preferably 22-29 mol %, more preferably from 23 to 28 mol %, particularly preferably from 24 to 27 mol %, especially about 25.2 mol % based on acrylic acid, a corresponding neutralization can also be achieved with other neutralizing agents;
  • ascorbic acid 0.005-0.006% by weight based on acrylic acid, preferably 0.0053-0.0058% by weight especially about 0.0056% by weight based on acrylic acid;
  • potassium peroxodisulfate 0.01-0.3% by weight based on acrylic acid, preferably 0.1-0.2% by weight, especially about 0.167% by weight based on acrylic acid;
  • useful crosslinkers further include other crosslinkers having at least 2 ethylenically unsaturated double bonds, for example ETMPTA (ethoxylated trimethylolpropane triacrylate (LAROMER® LR 9015 X from BASF AG) or polyethylene glycol 400 diacrylate): 0.2-0.5% by weight based on acrylic acid; what is decisive is that approximately the same degree of crosslinking is achieved.
  • ETMPTA ethoxylated trimethylolpropane triacrylate
  • LAROMER® LR 9015 X from BASF AG
  • polyethylene glycol 400 diacrylate 0.2-0.5% by weight based on acrylic acid
  • the resulting gel 2 is converted by drying into the base polymer 2.
  • sorbitan monococoate from 0 to 0.15% by weight based on acrylic acid, preferably 0.02-0.1% by weight, especially about 0.065% by weight based on acrylic acid;
  • potassium peroxodisulfate 0.01-0.3% by weight based on acrylic acid, preferably 0.1-0.2% by weight, especially about 0.167% by weight based on acrylic acid;
  • useful crosslinkers further include other crosslinkers having at least 2 ethylenically unsaturated double bonds, for example ETMPTA (ethoxylated trimethylolpropane triacrylate (LAROMER® LR 9015 X from BASF AG) or polyethylene glycol 400 diacrylate): 0.2-0.5% by weight based on acrylic acid; what is decisive is that approximately the same degree of crosslinking is achieved.
  • ETMPTA ethoxylated trimethylolpropane triacrylate
  • LAROMER® LR 9015 X from BASF AG
  • polyethylene glycol 400 diacrylate 0.2-0.5% by weight based on acrylic acid
  • NaHCO 3 35-55% by weight based on acrylic acid, preferably from 40 to 50% by weight, particular preferably from 43 to 46% by weight, especially about 44.5% by weight based on acrylic acid, a corresponding neutralization can also be achieved with other neutralizing agents;
  • useful crosslinkers further include other crosslinkers having at least 2 ethylenically unsaturated double bonds, for example ETMPTA (ethoxylated trimethylolpropane triacrylate (LAROMER® LR 9015 X from BASF AG) or polyethylene glycol 400 diacrylate): 0.2-0.5% by weight based on acrylic acid; what is decisive is that approximately the same degree of crosslinking is achieved.
  • ETMPTA ethoxylated trimethylolpropane triacrylate
  • LAROMER® LR 9015 X from BASF AG
  • polyethylene glycol 400 diacrylate 0.2-0.5% by weight based on acrylic acid
  • sodium persulfate 0.2-0.4% by weight based on acrylic acid, preferably 0.25-0.35% by weight, especially about 0.28% by weight based on acrylic acid;
  • Useful initiators further include other similarly acting systems or individual components, the above-indicated system preferably being initiated using a UV lamp. In the case of thermal initiation, appropriate initiator systems have to be used.
  • the resulting gel 5 is converted by drying into the base polymer 5.
  • Drying temperature of gel 120-200° C., preferably 140-180 C, especially about 160° C.
  • the crosslinking can be effected using allyl methacrylate: 0.005-1.0% by weight based on acrylic acid, preferably 0.1-0.5% by weight, particularly preferably 0.2-0.4% by weight, especially about 0.3% by weight based on acrylic acid;
  • the hydrophilicity of the particle surface of the hydrogel-forming polymer is additionally modified by formation of complexes.
  • the formation of complexes on the outer shell of the hydrogel particles is effected by spraying with solutions of divalent or more highly valent metal salt solutions, and the metal cations can react with the acid groups of the polymer to form complexes.
  • ethylene glycol diglycidyl ether 0.005-0.12% by weight based on dried gel (base polymer), preferably 0.01-0.05% by weight, especially about 0.03% by weight based on base polymer;
  • water 0.5-5% by weight based on base polymer, preferably 2-4% by weight, especially about 3.35% by weight based on base polymer;
  • 1,2-propanediol 0-4% by weight based on base polymer, preferably 0.5-3% by weight, especially about 1.5% by weight based on base polymer;
  • the pH of the hydrogel forming polymers according to the invention can be measured by the methods indicated in the description part and is 5.7 or less, especially 5.6, 5.5, 5.4, 5.3, 5.2 or 5.1 and less, preferably 5.0 especially 4.9, 4.8, 4.7 4.6 and less, particularly preferably 4.5; the lower limit is particularly preferably 4.4 especially 4.3, 4.2 or 4.1, preferably 4.0 especially 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1 or 3.0, preference being given to combinations of the upper and lower limits, for example pH values in the range from 3 to 5.7, preferably in the range from 4 to 5.5 and particularly preferably in the range from 4.4 to 4.6 or from 5.1 to 5.3.
  • the CRC value [g/g] of the hydrogel forming polymers according to the invention can be measured by the methods indicated in the description part and is preferably above 15, especially 16, 18, 20, 22, 24, or higher, particularly preferably 25, especially 26, 27, 28, 29, 30, 31, 32 or higher.
  • the PH AI value of the hydrogel forming polymers according to the invention can be measured and calculated by the methods indicated in the description part and is at least 80 or higher, especially 81, 82, 83, 84, 85, 86, 87, 88, 90 or higher, preferably above 91, especially 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117 118, 119, 120 or higher.
  • a combination of the threshold values for example PHAI with pH, PHAI with SFC, PHAI with CRC, PH AI with AUL, PHAI with Nessler, especially triple combinations such as PH AI with pH and SFC, PH AI with pH and CRC, PH AI with pH and AUL, PH AI with Nessler and SFC, PH AI with Nessler and CRC, PH AI with Nessler and AUL.
  • (D) optionally a tissue layer positioned directly above and below said core (C) and
  • (E) optionally an acquisition layer positioned between (A) and (C).
  • the liquid impervious layer (B) is generally a sheet of polyethylene or polypropylene.
  • the above constructions of the absorbent composition incorporate the highly swellable hydrogels at a weight fraction of from 10 to 100% by weight, preferably 20-100% by weight, more preferably 30-100% by weight, even more preferably 40-100% by weight, much more preferably 50-100% by weight, particularly preferably 60-100% by weight, especially preferably 70-100% by weight, extremely preferably 80-100% by weight and most preferably 90-100% by weight, based on the total weight of the construction and of the highly swellable hydrogels.
  • Examples of processes to obtain an absorbent composition comprising for example highly swellable hydrogels (c) embedded in a fiber material blend of synthetic fibers (a) and cellulose fibers (b), the blend ratio varying from (106 to 0) synthetic fiber : (0 to 100) cellulose fiber, include (1) a process where (a), (b) and (c) are mixed together at one and the same time, (2) a process where a mixture of (a) and (b) is mixed into (c), (3) a process where a mixture of (b) and (c) is mixed with (a), (4) a process where a mixture of (a) and (c) is mixed into (b), (5) a process where (b) and (c) are mixed and (a) is continuously metered in, (6) a process where (a) and (c) are mixed and (b) is continuously metered in, and (7) a process where (b) and (c) are mixed separately into (a).
  • processes (1) and (5) are preferred.
  • This method measures the free swellability of the hydrogel in a teabag.
  • 0.2000 ⁇ 0.0050 g of dried hydrogel (particle size fraction 106-850 ⁇ m) are weighed into a teabag 60 ⁇ 85 mm in size which is subsequently sealed.
  • the teabag is placed for 30 minutes in an excess of 0.9% by weight sodium chloride solution (at least. 0.83 l of sodium chloride solution/1 g of polymer powder).
  • the teabag is then centrifuged for 3. minutes at 250 g. The amount of liquid is determined by weighing back the centrifuged teabag.
  • the measuring cell for determining AUL 0.7 psi is a Plexiglass cylinder 60 mm in internal diameter and 50 mm in height. Adhesively attached to its underside is a stainless steel sieve bottom having a mesh size of 36 ⁇ m.
  • the measuring cell further includes a plastic plate having a diameter of 59 mm and a weight which can be placed in the measuring cell together with the plastic plate. The plastic plate and the weight together weigh 1,345 g.
  • AUL 0.7 psi is determined by determining the weight of the empty Plexiglass cylinder and of the plastic plate and recording it as W 0 .
  • a round filter paper 90 mm in diameter and ⁇ 20 ⁇ m in pore size (S&S 589 Schwarzband from Schleicher & Schüll) is subsequently placed on the ceramic plate.
  • the Plexiglass cylinder containing hydrogel forming polymer is then placed with plastic plate and weight on top of the filter paper and left there for 60 minutes. At the end of this period, the complete unit is removed from the Petri dish and subsequently the weight is removed from the Plexiglass cylinder.
  • the Plexiglass cylinder containing swollen hydrogel is weighed together with the plastic plate and the weight recorded as W b .
  • a Werner & Pfleiderer laboratory kneader having a working capacity of 2 l is evacuated to 980 mbar absolute by means of a vacuum pump and a previously separately prepared monomer solution which has been cooled to about 25° C. and inertized by passing nitrogen into it is sucked into the kneader.
  • the monomer solution has the following composition: 825.5 g of completely ion-free water, 431 g of acrylic acid, 120.68 g of NaOH 50%, 0.86 g of polyethylene glycol 400 diacrylate (SARTOMER® 344 from Cray Valley).
  • SARTOMER® 344 polyethylene glycol 400 diacrylate
  • a 10 l capacity polyethylene vessel thoroughly insulated with foamed plastic material is charged with 3 928 g of completely ion-free water, 630 g of sodium bicarbonate are suspended in the water, and 2 000 g of acrylic acid are added with stirring in such a way that the reaction solution does not foam over as a result of the onset of CO 2 evolution.
  • This is followed by the addition, in succession, of an emulsion of 1.3 g of sorbitan monococoate in 100 g of completely ion-free water and of 6.00 g of allyl methacrylate, and the solution is further inertized by passing nitrogen into it.
  • a 10 l capacity polyethylene vessel thoroughly insulated with foamed plastic material is charged with 4 046 g of completely ion-free water, 408 g of lithium hydroxide 1-hydrate are dissolved therein, and 2 000 g of acrylic acid are slowly added with stirring. This is followed by the addition, in succession, of an emulsion of 1.3 g of sorbitan monococoate in 100 g of completely ion-free water and of 8.1 g of allyl methacrylate, and the solution is further inertized by passing nitrogen into it.
  • the remaining AA can be rapidly admixed with ETMPA.
  • the monomer solution is cooled to 10° C. in an ice bath and admixed with 0.09 g of Darocur 1173: Irgacure 651 (2:1 ratio) photoinitiators, which are dissolved with stirring.
  • the monomer solution is cooled again to 10° C. in an ice bath and admixed with 6.832 g of 10% sodium persulfate solution (0.07 mol % based on AA).
  • the monomer solution is added in a 1.5 L glass vessel with temperature control.
  • the vessel is placed under a UV emission lamp (20 mWcm ⁇ 2 measured at vessel base). An exothermic polymerization is measured for 7.5 minutes, after which a transparent gel can be removed for further processing.
  • a Werner & Pfleiderer laboratory kneader having a working capacity of 2 1 is evacuated to 50 mbar by means of vacuum and a previously separately prepared monomer solution which has been cooled to about 25° C. and inertized by passing nitrogen into it is sucked into the kneader.
  • the monomer solution has the following composition: 3095.7 g of completely ion-free water, 1821.68 g of acrylic acid, 1012.05 g of NaOH 50%, 8.20 g of polyethylene glycol 400 diacrylate (Sartomer® 344 from CRAY VALLEY) and also 1.46 g of sorbitan monococoate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Colloid Chemistry (AREA)
US10/480,980 2001-06-28 2002-06-21 Acidic superabsorbent hydrogels Abandoned US20040180189A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US11/145,653 US20050234413A1 (en) 2001-06-28 2005-06-06 Acidic superabsorbent hydrogels
US11/706,906 US7915363B2 (en) 2001-06-28 2007-02-13 Acidic superabsorbent hydrogels
US11/872,815 US7790823B2 (en) 2001-06-28 2007-10-16 Acidic superabsorbent hydrogels

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10130671 2001-06-28
DE10130671.7 2001-06-28
DE10142138 2001-08-30
DE10142138.9 2001-08-30
DE10147713.9 2001-09-27
DE10147713 2001-09-27
PCT/EP2002/006877 WO2003002623A1 (de) 2001-06-28 2002-06-21 Saure hochquellfähige hydrogele

Related Child Applications (2)

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US11/145,653 Division US20050234413A1 (en) 2001-06-28 2005-06-06 Acidic superabsorbent hydrogels
US11/872,815 Continuation US7790823B2 (en) 2001-06-28 2007-10-16 Acidic superabsorbent hydrogels

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US20040180189A1 true US20040180189A1 (en) 2004-09-16

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US10/480,980 Abandoned US20040180189A1 (en) 2001-06-28 2002-06-21 Acidic superabsorbent hydrogels
US11/145,653 Abandoned US20050234413A1 (en) 2001-06-28 2005-06-06 Acidic superabsorbent hydrogels
US11/706,906 Expired - Fee Related US7915363B2 (en) 2001-06-28 2007-02-13 Acidic superabsorbent hydrogels
US11/872,815 Expired - Fee Related US7790823B2 (en) 2001-06-28 2007-10-16 Acidic superabsorbent hydrogels

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US11/145,653 Abandoned US20050234413A1 (en) 2001-06-28 2005-06-06 Acidic superabsorbent hydrogels
US11/706,906 Expired - Fee Related US7915363B2 (en) 2001-06-28 2007-02-13 Acidic superabsorbent hydrogels
US11/872,815 Expired - Fee Related US7790823B2 (en) 2001-06-28 2007-10-16 Acidic superabsorbent hydrogels

Country Status (7)

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US (4) US20040180189A1 (de)
EP (1) EP1425320B1 (de)
JP (1) JP2004530777A (de)
AT (1) ATE340199T1 (de)
DE (1) DE50208214D1 (de)
ES (1) ES2271287T3 (de)
WO (1) WO2003002623A1 (de)

Cited By (29)

* Cited by examiner, † Cited by third party
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US20050075617A1 (en) * 2003-10-06 2005-04-07 Sca Hygiene Products Ab Absorbent article comprising an absorbent structure
US20050113252A1 (en) * 2003-09-05 2005-05-26 Koji Miyake Method of producing particle-shape water-absorbing resin material
US20060034935A1 (en) * 2004-07-22 2006-02-16 Pronovost Allan D Compositions and methods for treating excessive bleeding
US20060173431A1 (en) * 2005-02-01 2006-08-03 Laumer Jason M Absorbent articles comprising polyamine-coated superabsorbent polymers
US20060173433A1 (en) * 2005-02-01 2006-08-03 Laumer Jason M Absorbent articles comprising polyamine-coated superabsorbent polymers
US20060173432A1 (en) * 2005-02-01 2006-08-03 Laumer Jason M Absorbent articles comprising polyamine-coated superabsorbent polymers
US20070093767A1 (en) * 2005-10-21 2007-04-26 Giovanni Carlucci Absorbent article having improved absorption and retention capacity for proteinaceous or serous body fluids
US20070203304A1 (en) * 2004-03-30 2007-08-30 Basf Aktiengesellschaft Method Of Manufacturing Superabsorbent Polymers
US20070208315A1 (en) * 2006-03-03 2007-09-06 The Procter & Gamble Company Thermoplastic absorbent material having increased absorption and retention capacity for proteinaceous or serous body fluids
US7285615B2 (en) 2003-09-02 2007-10-23 Nippon Shokubai Co., Ltd. Particulate water-absorbent resin composition
US20080091159A1 (en) * 2005-10-21 2008-04-17 Giovanni Carlucci Absorbent article having increased absorption and retention capacity for proteinaceous or serous body fluids
US20080119808A1 (en) * 2004-11-17 2008-05-22 Masayoshi Handa Water Absorbing Resin Particle And, Making Use Of The Same, Absorber Material And Absorbent Article
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US20050234413A1 (en) 2005-10-20
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US7790823B2 (en) 2010-09-07
DE50208214D1 (de) 2006-11-02
ES2271287T3 (es) 2007-04-16
US20070149716A1 (en) 2007-06-28
ATE340199T1 (de) 2006-10-15
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EP1425320B1 (de) 2006-09-20
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