EP1363682A1 - Hydrogels revetus de separateurs steriques ou electrostatiques - Google Patents

Hydrogels revetus de separateurs steriques ou electrostatiques

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Publication number
EP1363682A1
EP1363682A1 EP01985933A EP01985933A EP1363682A1 EP 1363682 A1 EP1363682 A1 EP 1363682A1 EP 01985933 A EP01985933 A EP 01985933A EP 01985933 A EP01985933 A EP 01985933A EP 1363682 A1 EP1363682 A1 EP 1363682A1
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EP
European Patent Office
Prior art keywords
water
hydrogels
acid
coated
spacers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01985933A
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German (de)
English (en)
Inventor
Volker Frenz
Norbert Herfert
Ulrich Riegel
William E. Volz
Thomas H. Majette
James M. Hill
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1363682A1 publication Critical patent/EP1363682A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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

Definitions

  • the invention relates to hydrogels, water-absorbing compositions containing them, processes for their preparation, their use in hygiene articles and processes for determining suitable water-absorbing compositions.
  • the current trend in diaper construction is towards producing even thinner constructions with a reduced cellulose fiber content and an increased hydrogel content.
  • the advantage of thinner constructions is not only evident in improved wearing comfort, but also in reduced packaging and storage costs.
  • the requirement profile for the water-swellable hydrophilic polymers has changed significantly.
  • the ability of the hydrogel to transfer and distribute fluids is now critical. Due to the higher loading of the hygiene article (polymer per unit area), the polymer in the swollen state must not form a barrier layer for the subsequent liquid (gel blocking). Gel blocking occurs when liquid wets the surface of the highly absorbent hydrogel particles and the outer shell swells. As a result, a barrier layer is formed which makes it difficult for liquids to diffuse into the interior of the particle and thus leads to leakage. If the product has good gel permeability and thus good transport properties, optimal utilization of the entire hygiene article can be guaranteed.
  • the absorption capacity and gel strength were optimized by specifically adjusting the degree of crosslinking in the starting polymer and subsequent postcrosslinking. Improved gel permeability values can only be generated if a higher crosslinking density is permitted in the starting polymer. However, higher crosslinking densities simultaneously mean a reduction in the absorption capacity and a decrease in the swelling rate in the polymer. As a result, additional layers have to be introduced in order to prevent leakage while simultaneously increasing the hydrogel content in the hygiene article to prevent, which in turn leads to bulky hygiene articles and counteracts the actual objective, the production of thinner hygiene products.
  • a possible way of achieving improved transport properties and avoiding gel blocking is to shift the grain size spectrum to higher values. However, this leads to a decrease in the swelling rate since the surface of the absorbent material is reduced. This is undesirable.
  • Another method of achieving improved gel permeability is surface post-crosslinking, which gives the hydrogel body a higher gel strength when swollen. Gels with only a low gel strength can be deformed under an applied pressure (body pressure), clog pores in the hydrogel / cellulose fiber absorbent body and thereby prevent further fluid absorption. Since an increase in the crosslinking density in the starting polymer can be ruled out for the above reasons, the surface postcrosslinking represents an elegant method for increasing the gel strength.
  • the surface postcrosslinking increases the crosslinking density in the shell of the hydrogel particles, which increases the absorption under pressure (Absorbency Under Load AUL). of the base polymer generated in this way is raised to a higher level. While the absorption capacity in the hydrogel shell decreases, the core of the hydrogel particles has an improved absorption capacity compared to the shell due to the presence of movable polymer chains, so that the shell structure ensures improved liquid transmission.
  • hydrogel particles touch one another in the swollen state when large amounts are used and thus form a closed absorption layer within which the liquid distribution takes place.
  • a subsequent modification of the surface of the base polymers surface post-crosslinked starting polymers
  • DE-A-3 523 617 relates to the addition of finely divided amorphous polysilicic acids (silica) to dry hydrogel powder after the surface postcrosslinking with crosslinking agents which react with carboxyl groups.
  • aluminum sulfate is used as the sole crosslinking agent or in combination with another crosslinking agent for surface postcrosslinking.
  • WO 95/22356 relates to the modification of absorbent polymers with other polymers to improve the absorption properties.
  • Preferred modifiers are polyamines and polyimines.
  • the effects with regard to SFC are small according to Tables 1 and 2.
  • WO 95/26209 relates to absorbent structures which have at least one region which contains 60-100% highly swellable hydrogel, the highly swellable hydrogel having an SFC of at least 30 x 10 "7 cm 3 s / g and a PUP 0.7 psi of at least 23 g
  • SFC SFC of at least 30 x 10 "7 cm 3 s / g
  • PUP 0.7 psi of at least 23 g
  • the SFC increases with increasing grain size of the highly swellable hydrogel.
  • the surface of the highly swellable hydrogel particles decreases in comparison to their volume, which results in a decrease in the swelling rate. It can therefore be deduced from the results of this series of experiments that the swelling rate also shows a reciprocal dependence on the SFC.
  • non-water-soluble water-swellable hydrogels which are coated with steric or electrostatic spacers, the hydrogels having the following features before coating:
  • AUL Absorption under pressure
  • coated hydrogels preferably have the following features:
  • Centrifuge retention capacity of at least 24 g / g
  • Saline Flow Conductivity of at least 30 x 10 "7 , preferably at least 60 x 10 " 7 cm 3 s / g and
  • FSR Free Swell Rate
  • water-absorbent refers to water and aqueous systems which can contain dissolved organic and inorganic compounds, in particular to body fluids such as urine, blood or fluids containing them.
  • the hydrogels according to the invention and water-absorbing compositions containing them can be used for the production of hygiene articles or other articles which serve to absorb aqueous liquids.
  • the invention thus further relates to hygiene articles which contain a water-absorbing composition according to the invention between a liquid-permeable cover sheet and a liquid-impermeable back sheet.
  • the hygiene articles can be in the form of diapers, sanitary napkins and incontinence products.
  • the invention also relates to a method for improving the performance profile of water-absorbent compositions by increasing the permeability, capacity and swelling rate of the water-absorbent compositions by using non-water-soluble water-swellable hydrogels, as defined above.
  • the invention also relates to a method for determining water-absorbent compositions with high permeability, capacity and swelling rate by measuring the absorption under pressure (AUL) and the gel strength for uncoated hydrogels and determining the centrifuge retention capacity (CRC), saline flow conductivity (SFC) and free Swell rate (FSR) of the coated hydrogels for a given water-absorbing composition and determination of the water-absorbing composition for which the hydrogels show the property spectrum mentioned above.
  • AUL absorption under pressure
  • CRC centrifuge retention capacity
  • SFC saline flow conductivity
  • FSR free Swell rate
  • the invention relates to the use of hydrogels, as defined above, in hygiene articles or other articles which serve to absorb aqueous liquids, to increase the permeability, capacity and swelling rate.
  • base polymers which have an AUL (0.7 psi) of at least 20 g / g, preferably of at least 22 g / g, particularly preferably of at least 24 g / g , extremely preferably of at least 26 g / g, and a gel strength of at least 1600 Pa, preferably of at least 1800 Pa, particularly preferably of at least 2000 Pa, the surface of which is subsequently coated with a steric (inert) or electrostatic spacer. Base polymers with these properties ensure that the spacer effect is not compensated for by the gel particle being too easy to deform under pressure.
  • hydrogels with electrostatic spacers also have an improved connection to cellulose fibers, since the latter are weakly negatively charged on the surface. This fact is particularly advantageous, since said property profile of hydrogels with electrostatic spacers and cellulose fibers enables an absorption layer to be produced without additional aids, which fix the hydrogel within the fiber matrix.
  • the attachment to the cellulose fibers automatically fixes the hydrogel material so that there is no undesired redistribution of the hydrogel material, for example to the surface of the absorbent core.
  • the highly swellable polymer particles according to the invention are notable for high absorption capacities, improved liquid transport performance and higher swelling speed. For this reason, the hygiene article can be made extremely thin become.
  • the increased proportion of highly swellable hydrogels according to the invention with high capacity enables enormous absorption capacities, so that the problem of leakage is avoided. At the same time, the high absorption capacity is fully exploited by the improved liquid distribution.
  • the present invention relates to the production of novel, highly swellable hydrogels by
  • (1) preselection of highly swellable base polymers which have an AUL (0.7 psi) of at least 20 g / g, preferably of at least 22 g / g, particularly preferably of at least 24 g / g, extremely preferably of at least 26 g / g, and have a gel strength of at least 1600 Pa, preferably of at least 1800 Pa, particularly preferably of at least 2000 Pa.
  • hydrogels are generated with the following combinations of properties:
  • SFC greater than or equal to 30 x 10 '7 cm 3 s / g, preferably greater than or equal to 60 x 10 "7 cm 3 s / g, preferably greater than or equal to 80 x 10 " 7 cm 3 s / g, more preferably greater than or equal to 100 x 10 " 7 cm s / g, even more preferably greater than or equal to 120 x 10 " cm s / g, particularly preferably greater than or equal to 150 x 10 " 7 cm 3 s / g, extremely preferably greater than or equal to 200 x 10 "7 cm 3 s / g am most preferably greater than or equal to 300 x 10 "7 cm 3 s / g and - Free Swell Rate greater than or equal to 0.15 g / gs, preferably greater than or equal to 0.20 g / gs, more preferably greater than 0.30 g / gs, even more preferably greater than or equal to 0.50 g / gs, particularly
  • Vortex time less than or equal to 160 s preferably vortex time less than or equal to 120 s, more preferably vortex time less than or equal to 90 s, particularly preferably vortex time less than or equal to 60 s, most preferably vortex time less than or equal to 30 s.
  • Hydrogel-forming 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 carboxymethyl cellulose, partially crosslinked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives, alginates and carrageenans.
  • Suitable graft bases can be of natural or synthetic origin. Examples are starch, cellulose or cellulose derivatives and other polysaccharides and oligosaccharides, polyvinyl alcohol, polyalkylene oxides, in particular polyethylene oxides and polypropylene oxides, polyamines, polyamides and hydrophilic polyesters. Suitable polyalkylene oxides have, for example, the formula
  • R 1 and R 2 independently of one another are hydrogen, alkyl, alkenyl or acrylic,
  • X is hydrogen or methyl and n is an integer from 1 to 10,000.
  • R 1 and R 2 are preferably hydrogen, (Ci - C 4 ) alkyl, (C 2 - C 6 ) alkenyl or phenyl.
  • Preferred hydrogel-forming polymers are crosslinked polymers with acid groups which are predominantly in the form of their salts, generally alkali metal or ammonium salts, available. Such polymers swell particularly strongly into gels on contact with aqueous liquids.
  • Polymers which are obtained by crosslinking polymerization or copolymerization of acid-bearing monoethylenically unsaturated monomers or their salts are preferred. It is also possible to (co) polymerize these monomers without crosslinking agents and to subsequently crosslink them.
  • Such monomers bearing acid groups are, for example, monoethylenically unsaturated C 3 -C 25 -carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
  • monoethylenically unsaturated C 3 -C 25 -carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
  • monoethyl-unsaturated sulfonic or phosphonic acids for example vinylsulfonic acid, allylsulfonic acid, sulfoethylacrylate, sulfomethacrylate, sulfopropylacrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, Acrylamido-2-methyl-propanesulfonic acid.
  • the monomers can be used alone or as a mixture with one another.
  • Preferred monomers are acrylic acid, methacrylic acid, vinyl sulfonic acid, acrylamidopropanesulfonic acid or mixtures of these acids, e.g. B. mixtures of acrylic acid and methacrylic acid, mixtures of acrylic acid and acrylamidopropanesulfonic acid or mixtures of acrylic acid and vinylsulfonic acid.
  • additional monoethylenically unsaturated compounds which do not carry acid groups but can be copolymerized with the monomers bearing acid groups.
  • monoethylenically unsaturated carboxylic acids e.g. B. acrylamide, methacrylamide and N-vinylformamide, N-vinyl acetamide, N-methyl-vinyl acetamide, acrylonitrile and methacrylonitrile.
  • Suitable compounds are, for example, vinyl esters of saturated C 1 -C 4 -carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate, alkyl vinyl ethers having at least 2 C atoms in the alkyl group, such as ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C 3 -C 6 -carboxylic acids , e.g. B. esters of monohydric - to C 18 alcohols and acrylic acid, methacrylic acid or maleic acid, half-ester of maleic acid, for. B.
  • vinyl esters of saturated C 1 -C 4 -carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate
  • alkyl vinyl ethers having at least 2 C atoms in the alkyl group such as ethyl vinyl ether or butyl vinyl ether
  • N-vinyl lactams such as N-vinyl pyrrolidone or N-vinyl caprolactam
  • acrylic acid and methacrylic acid esters of alkoxylated monohydric, saturated alcohol len e.g. B. of alcohols with 10 to 25 carbon atoms, which have been reacted with 2 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol
  • Other suitable monomers are styrene and alkyl-substituted styrenes such as ethylstyrene or tert-butylstyrene.
  • Crosslinked polymers from monoethylenically unsaturated monomers bearing acid groups are preferred, which are optionally converted into their alkali or ammonium salts before or after the polymerization, and from 0-40% by weight, based on their total weight, of monoethylenically unsaturated monomers bearing no acid groups.
  • Crosslinked polymers of monoethylenically unsaturated C 3 -C 12 -carboxylic acids and / or their alkali metal or ammonium salts are preferred.
  • crosslinked polyacrylic acids are preferred, the acid groups of which are 25-100% in the form of alkali or ammonium salts.
  • Polyethylene glycol dimethacrylates which are each derived from polyethylene glycols having a molecular weight of from 106 to 8500, preferably 400 to 2000, derived, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate propylene glycol dimethacrylate, butane diol diacrylate is, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, allyl methacrylate, diacrylates and dimethacrylates of Block copolymers of ethylene oxide and propylene oxide, polyhydric alcohols esterified two or more times with acrylic acid or methacrylic acid, such as glycerol or pentaerythritol, triallylamine, dialkyldiallylammonium halides such as dimethyldiallyl
  • Pentaerythritol triallyl ether reaction products of 1 mole of ethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether with 2 moles of pentaerythritol triallyl ether or allyl alcohol, and / or divinylethylene urea.
  • water-soluble crosslinking agents are used, e.g. B.
  • crosslinkers are compounds which contain at least one polymerizable ethylenically unsaturated group and at least one further functional group.
  • the functional group of these crosslinkers must be able to react with the functional groups, essentially the acid groups, of the monomers. Suitable functional groups are, for example, hydroxyl, amino, epoxy and aziridino groups. Can be used for.
  • N-vinylimidazoles such as N-vinylimidazole, l-vinyl-2-methylimidazole, and N-vinylimidazolines
  • N-vinylimidazoline such as 1-VinyI-2-ethylimidazoline or 1-vinyl-2-propylimidazoline, which can be used in the polymerization in the form of the free bases, in quaternized form or as a salt.
  • Dialkylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate are also suitable.
  • the basic esters are preferably used in quaternized form or as a salt.
  • Glycidyl (meth) acrylate can also be used.
  • crosslinkers are compounds which contain at least two functional groups which are able to react with the functional groups, essentially the acid groups of the monomers.
  • the functional groups suitable for Merfur have already been mentioned above, ie hydroxyl, amino, epoxy, isocyanate, ester, amido and aziridino groups.
  • crosslinkers examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, polyglycerol, triethanolamine, propylene glycol, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, ethanolamine, Sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, trimethylolpropane, pentaerythritol, 1,3-butanediol, 1,4-butanediol, polyvinyl alcohol, sorbitol, starch, polyglycidyl ethers such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
  • Glycerol diglycidyl ether glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether,
  • Polyaziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylene diethylene urea, diphenylmethane-bis-4,4'-N, N'-di-ethylene urea, halo epoxy compounds such as epichlorohydrin and ⁇ -Methylpifluor- hydrin, polyisocyanates such as 2,4-tolylene diisocyanate and hexamethylene diisocyanate, alkylene carbonates such as l, 3-dioxolan-2-one and 4-methyl-l, 3-dioxolan-2-one, further bisoxazolines and oxazolidones, polyamidoamines and their reaction products with epichlorohydrin, also polyquaternary amines such as condensation products of dimethylamine with epichlorohydrin, homo- and copolymers of diallyldimethylammonium chloride and homo- and
  • the crosslinkers are present in the reaction mixture, for example from 0.001 to 20% by weight and preferably from 0.01 to 14% by weight.
  • the polymerization is initiated as usual by an initiator. It is also possible to initiate the polymerization by the action of electron beams on the polymerizable, aqueous mixture. However, the polymerization can also be initiated in the absence of initiators of the type mentioned above by exposure to high-energy radiation in the presence of photoinitiators. All compounds which decompose into free radicals under the polymerization conditions can be used as polymerization initiators, e.g. B. peroxides, hydroperoxides, hydrogen peroxides, persulfates, azo compounds and the so-called redox catalysts. The use of water-soluble initiators is preferred. In some cases it is advantageous to use mixtures of different polymerization initiators, e.g. B.
  • Suitable organic peroxides are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert.-butyl perisobutyrate, tert.-butyl per-2-ethyl hexanoate, tert-butanoate .-Butyl permaleate, tert.-butyl perbenzoate, di- (2- ethylhexyl) peroxidicarbonate, dicyclohexylperoxidicarbonate, di- (4-tert-butylcyclohe
  • Particularly suitable polymerization initiators are water-soluble azo starters, e.g. B. 2,2'-azo-bis (2-amidinopropane) dihydrochloride, 2,2'-azobis- (N, N'-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis [2- (2'-imidazolin-2-yl) propane] dihydrochloride and 4,4'-azobis (4-cyanovaleric acid).
  • the polymerization initiators mentioned are used in conventional amounts, e.g. B. in amounts of 0.01 to 5, preferably 0.05 to 2.0 wt .-%, based on the monomers to be polymerized.
  • Redox catalysts are also suitable as initiators.
  • the redox catalysts contain at least one of the above-mentioned per compounds as the oxidizing component and as reducing component, for example, ascorbic acid, glucose, sorbose, ammonium or alkali metal bisulfite, sulfite, thiosulfate, hyposulfite, pyro-sulfite or sulfide, metal salts, such as iron ( II) ions or sodium hydroxymethyl sulfoxylate.
  • Ascorbic acid or sodium sulfite is preferably used as the reducing component of the redox catalyst.
  • photoinitiators are usually used as initiators. These can be, for example, so-called ⁇ -splitters, H-abstracting systems or also azides.
  • initiators are benzophenone derivatives such as Michler's ketone, phenanthrene derivatives, fluorene derivatives, anthraquinone derivatives, thioxanone derivatives, coumarin derivatives, benzoin ethers and their derivatives, azo compounds such as the radical formers mentioned above, substituted hexaarylbisimidazoles or acylphosphine oxides.
  • azides examples include 2- (N, N-dimethylamino) ethyl 4-azidocinnamate, 2- (N, N-dimethylamino) ethyl 4-azidonaphthyl ketone, 2- (N, N-
  • the photoinitiators are usually used in amounts of from 0.01 to 5% by weight, based on the monomers to be polymerized.
  • polymers which have been prepared by the polymerization of the abovementioned monoethylenically unsaturated acids and, if appropriate, monoethylenically unsaturated comonomers and which have a molecular weight greater than 5000, preferably greater than 50,000 are reacted with compounds which have at least two groups reactive towards acid groups. This reaction can take place at room temperature or at elevated temperatures up to 220 ° C.
  • the suitable functional groups have already been mentioned above, i.e. Hydroxyl, amino, epoxy, isocyanate, ester, amido and aziridino groups, as well as examples of such crosslinkers.
  • crosslinkers are added to the acid-bearing polymers or salts in amounts of 0.5 to 25% by weight, preferably 1 to 15% by weight, based on the amount of the polymer used.
  • the crosslinked polymers are preferably used in neutralized form. However, the neutralization can also have been carried out only partially.
  • the degree of neutralization is preferably 25 to 100%, in particular 50 to 100%.
  • Possible neutralizing agents are: alkali metal bases or ammonia or amines.
  • Sodium hydroxide solution or potassium hydroxide solution is preferably used.
  • the neutralization can also be carried out with the aid of sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate or other carbonates or hydrogen carbonates or ammonia.
  • primary, secondary and tertiary amines can be used.
  • aqueous solution Polymerization in aqueous solution is preferred as so-called gel polymerization. 10 to 70% by weight aqueous solutions of the monomers and, if appropriate, a suitable graft base are polymerized in the presence of a radical initiator using the Trommsdorff-Norrish effect.
  • the polymerization reaction can be carried out in the temperature range between 0 ° C. and 150 ° C., preferably between 10 ° C. and 100 ° C., both under normal pressure and under elevated or reduced pressure.
  • the polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.
  • the quality properties of the polymers can be improved further by reheating the polymer gels for several hours, for example in the temperature range from 50 to 130 ° C., preferably from 70 to 100 ° C.
  • Hydrogel-forming polymers which are post-crosslinked on the surface are preferred.
  • the surface postcrosslinking can take place in a manner known per se with dried, ground and sieved polymer particles.
  • compounds which can react with the functional groups of the polymers with crosslinking are preferably applied to the surface of the hydrogel particles in the form of a water-containing solution.
  • the water-containing solution can contain water-miscible organic solvents. Suitable solvents are alcohols such as methanol, ethanol, i-propanol or acetone.
  • Suitable post-crosslinking agents are, for example
  • Di- or polyglycidyl compounds such as phosphonic acid diglycidyl ether or ethylene glycol diglycidyl ether, bischlorohydrin ether of polyalkylene glycols,
  • Polyols such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, glycerol, methyltriglycol, polyethylene glycols with an average molecular weight M w of 200-10000, di- and polyglycerol, pentaerythritol, sorbitol, the oxyethylates of these polyols and their esters with carboxylic acids or carbonic acid such as ethylene carbonate or propylene carbonate,
  • Carbonic acid derivatives such as urea, thiourea, guanidine, dicyandiamide, 2-oxazolidinone and its derivatives, bisoxazoline, polyoxazolines, di- and
  • Di- and poly-N-methylol compounds such as methylenebis (N-methylol-methacrylamide) or melamine-formaldehyde resins, Compounds with two or more blocked isocyanate groups such as, for example, trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethyl-piperidinone-4.
  • acidic catalysts such as p-toluenesulfonic acid, phosphoric acid, boric acid or ammonium dihydrogen phosphate can be added.
  • Particularly suitable post-crosslinking agents are di- or polyglycidyl compounds such as ethylene glycol diglycidyl ether, the reaction products of polyamidoamines with epichlorohydrin and 2-oxazolidinone.
  • the crosslinking agent solution is preferably applied by spraying on a solution of the crosslinking agent in conventional reaction mixers or mixing and drying systems such as Patterson-Kelly mixers, DRAIS turbulence mixers, Lödige mixers,
  • Spraying the crosslinker solution can be followed by a temperature treatment step, preferably in a downstream dryer, at a temperature between 80 and 230 ° C, preferably 80-190 ° C, and particularly preferably between 100 and 160 ° C, over one
  • Solvent components can be removed. However, drying can also take place in the mixer itself, by heating the jacket or by blowing in a preheated carrier gas.
  • Inert materials such as, for example, silicates with a band, chain or leaf structure (montmorillonite, kaolinite, talc), zeolites, activated carbons or polysilicic acids, can act as steric spacers.
  • Other inorganic inert spacers are, for example, magnesium carbonate, calcium carbonate, barium sulfate, aluminum oxide, titanium dioxide and iron (II) oxide.
  • polyalkyl methacrylates or thermoplastics such as polyvinyl chloride can act as inert organic-based spacers.
  • Polysilicic acids are preferably used which, depending on the type of production, differentiate between precipitated silica and pyrogenic silicas.
  • AEROSIL ® pyrogenic silicas
  • Silica FK sipernat ®
  • Wessalon ® precipitated silicas.
  • siloxane and silanol groups on the surface of the silica particles.
  • the siloxane groups predominate in number. They are largely the cause of that inert character of this synthetic silica.
  • Special types of silica are available for different applications.
  • the surface of the silicic acid can be chemically modified by adding silane, so that originally hydrophilic silicic acid forms hydrophobic variants.
  • Some types of silica are present as mixed oxides, for example in a mixture with aluminum oxide.
  • the spacer function can be controlled depending on the surface properties of the primary particles. Fumed silica (e.g. AEROSIL ® ) is available in grain fractions from 7 to 40 nm.
  • Silica under the trade names Silica FK, Sipernat ® , Wessalon ® can be obtained as a powder with a grain size of 5 to 100 ⁇ m and a specific surface area of 50 - 450 m 2 / g.
  • the particle size of the inert powders is preferably at least 1 ⁇ m, more preferably at least 4 ⁇ m, particularly preferably at least 20 ⁇ m and extremely preferably at least 50 ⁇ m.
  • the use of precipitated silicas is particularly preferred.
  • the base polymers coated with inert spacer material can be produced by applying the inert spacers in an aqueous or water-miscible medium or by applying the inert spacers in powder form to powdery base polymer material.
  • the aqueous or water-miscible media are preferably applied by spraying onto dry polymer powder.
  • pure powder / powder mixtures are produced from powdery inert spacer material and base polymer.
  • the inert spacer material is used in a proportion of 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight, particularly preferably 0.3 to 1% by weight, based on the total weight of the coated hydrogel, applied to the surface of the base polymer.
  • Cationic components can be added as electrostatic spacers.
  • Polyquaternary amines can also be synthesized by reacting dimethyl sulfate with polymers such as polyethyleneimines, copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate or copolymers of ethyl methacrylate and diethylaminoethyl methacrylate.
  • polymers such as polyethyleneimines, copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate or copolymers of ethyl methacrylate and diethylaminoethyl methacrylate.
  • the polyquaternary amines are available in a wide range of molecular weights.
  • Electrostatic spacers are also generated by applying a cross-linked, cationic shell, either by means of Regenzien, which can form a network with itself, such as. B. addition products of epichlorohydrin to polyamidoamines, or by the application of cationic polymers which can react with an added crosslinker, e.g. B. polyamines or polyimines in combination with polyepoxides, multifunctional esters, multifunctional acids or multifunctional (meth) acrylates. All multifunctional amines with primary or secondary ammo groups can be used, e.g. polyethyleneimine, polyallylamine, polylysine, preferably polyvinylamine.
  • polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and polyethyleneimines, and polyamines with molecular weights of up to 4,000,000 each.
  • Electrostatic spacers can also be applied by adding solutions of di- or polyvalent metal salt solutions.
  • divalent or polyvalent metal cations are Mg 2+ , Ca 2+ , Al 3+ , Sc 3+ , Ti 4+ , Mn 2+ , Fe 2 + / 3 + , Co 2+ , Ni 2+ , Cu + 2+ , Zn 2+ , Y 3+ , Zr 4+ , Ag + , La 3+ , Ce 4+ , Hf 4+ , and Au + 3+
  • preferred metal cations are Mg 2+ , Ca 2+ , Al 3+ , Ti 4+ , Zr 4+ and La 3+
  • particularly preferred metal cations are Al 3+ , Ti 4+ and Zr 4+ .
  • the metal cations can be used either alone or in a mixture with one another. Of the metal cations mentioned, all metal salts are suitable which have sufficient solubility in the solvent to be used. Metal salts with weakly complexing amones such as chloride, nitrate and sulfate are particularly suitable. Water, alcohols, DMF, DMSO and mixtures of these components can be used as solvents for the metal salts become. Water and water / alcohol mixtures, such as water / methanol or water / 1,2-propanediol, are particularly preferred.
  • the electrostatic spacers can be applied by application in an aqueous or water-miscible medium.
  • aqueous or water-miscible medium is the preferred production variant when adding metal salts.
  • Cationic polymers are applied by applying an aqueous solution or in a water-miscible solvent, optionally also as a dispersion, or else by applying in powder form on powdery base polymer material.
  • the aqueous or water-miscible media are preferably applied by spraying onto dry polymer powder.
  • the polymer powder can then optionally be dried.
  • the coated base polymers are only dried at temperatures of up to 100 ° C.
  • the cationic spacers are used in a proportion of 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight, particularly preferably 0.1 to 1% by weight, based on the total weight of the coated hydrogel, applied to the surface of the base polymer.
  • hydrogels mentioned are distinguished by a high absorption capacity for water and aqueous solutions and are therefore preferably used as absorbents in hygiene articles.
  • the water-swellable hydrogels can be present in connection with a carrier material for the hydrogels, preferably embedded as particles in a polymer fiber matrix or an open-pore polymer foam, fixed to a flat carrier material or present as particles in chambers formed from a carrier material.
  • the invention also relates to a process for the preparation of the water-absorbent compositions
  • hydrogels into a polymer fiber matrix or open-pore polymer foam or into a chamber formed from a carrier material or fixing them to a flat carrier material.
  • the hygiene articles which can be produced from the water-absorbing compositions according to the invention are known and described per se. They are preferably diapers, sanitary napkins and incontinence products such as incontinence pads. The structure of corresponding products is known.
  • This method determines the free swellability of the hydrogel in the tea bag.
  • 0.2000 ⁇ 0.0050 g of dried hydrogel (grain fraction 106 - 850 ⁇ m) are weighed into a 60 x 85 mm tea bag, which is then sealed.
  • the tea bag is placed in an excess of 0.9% by weight saline solution (at least 0.83 1 saline solution / l g polymer powder) for 30 minutes.
  • the tea bag is then centrifuged at 250 g for 3 minutes. The amount of liquid is determined by weighing the centrifuged tea bag.
  • the measuring cell for determining the AUL 0.7 psi is a plexiglass cylinder with an inner diameter of 60 mm and a height of 50 mm, which has a glued-on stainless steel sieve bottom with a mesh size of 36 ⁇ m on the underside.
  • the measuring cell also includes a plastic plate with a diameter of 59 mm and a weight which can be placed together with the plastic plate in the measuring cell. The weight of the plastic plate and the weight together are 1345 g.
  • the weight of the empty plexiglass cylinder and the plastic plate is determined and noted as W 0 .
  • a ceramic filter plate with a diameter of 120 mm and a porosity of 0 is placed and 0.9% by weight sodium chloride solution is filled in so that the liquid surface is flush with the filter plate surface without the surface of the filter plate wetting becomes.
  • a round filter paper with a diameter of 90 mm and a pore size ⁇ 20 ⁇ m (S&S 589 black tape from Schleicher & Schüll) is then placed on the ceramic plate.
  • the plexiglass cylinder containing the hydrogel-forming polymer is now placed with the plastic plate and weight on the filter paper and left there for 60 minutes.
  • the complete unit is removed from the Petri dish from the filter paper and then the weight is removed from the Plexiglas cylinder.
  • the plexiglass cylinder containing swollen hydrogel is weighed out together with the plastic plate and the weight is noted as W b .
  • the absorption under pressure (AUL) is calculated as follows:
  • a synthetic urine replacement solution which can be prepared by dissolving 2.0 g KC1, 2.0 g Na 2 SO 4 , 0.85 g NH 4 H 2 PO 4 , 0.15 g ( NH 4 ) 2 HPO 4 , 0.19 g CaCl 2 and 0.23 g MgCl 2 in 1 liter of distilled water, added to the center of the plastic dish.
  • the rheological tests to determine the gel strength are carried out on the Controlled Stress Rheometer CSL 100 from Carrimed. All measurements are made at room temperature.
  • the gel strength is determined using the oscillation mode on the CS rheometer from Carrimed using a plate-plate geometry (diameter 6 cm). To avoid the slip effect, sandblasted plate systems are used for this purpose. The sample is placed on the platter and the ramp is slowly raised to allow the gap to close slowly. The measuring gap is 1 mm and must be completely filled with sample material.
  • the gel strength denotes the modulus of elasticity of the pre-swollen hydrogel and is measured analogously to this in the linear viscoelastic area of the sample, which is determined in a preliminary test on the same sample.
  • the applied torque is gradually increased within the linear viscoelastic range (torque sweep, torque curve) in oscillation mode at constant frequency (1 Hz).
  • a straight line is obtained as a measurement curve, which quantifies the gel strength as the material constant of the elastic solid.
  • the present measured values are mean values (number average) from 3 test series.
  • 3600 g of demineralized water and 1400 g of acrylic acid are placed in a polyethylene vessel with a capacity of 10 l, which is well insulated by foamed plastic material. Now 4.0 g of tetraallyloxyethane and 5.0 g of AUyl methacrylate are added.
  • the initiators consisting of 2.2 g of 2,2'-azobisamidinopropane dihydrochloride, dissolved in 20 g of deionized water, 4 g of potassium peroxodisulfate, dissolved in 150 g of deionized water and 0.4 g Ascorbic acid, dissolved in 20 g of demineralized water, added successively and stirred.
  • reaction solution is then left to stand without stirring, a solid gel being formed by the onset of polymerization, in the course of which the temperature rises to approximately 90 ° C.
  • This is then mechanically crushed, adjusted to a pH of 6.0 by adding 50% by weight sodium hydroxide solution.
  • the gel is then dried, ground and sieved to a particle size distribution of 100-850 ⁇ m. 1 kg of this dried hydrogel is sprayed in a ploughshare mixer with a solution consisting of 60 g of demineralized water, 40 g of i-propanol and 1.0 g of ethylene glycol diglycidyl ether and then heat-treated at 140 ° C. for 60 minutes.
  • the product described here has the following properties:
  • the initiators 6.0 g of 2,2'-azobisamidinopropane dihydrochloride, dissolved in 60 g of deionized water, 12 g of potassium peroxodisulfate, dissolved in 450 g of deionized water, and 1.2 g of ascorbic acid are dissolved at a temperature of 4.degree in 50 g of demineralized water, added in succession and stirred well.
  • the reaction solution is then left to stand without stirring, a gel being formed by the onset of polymerization, in the course of which the temperature rises to approximately 85.degree. This is then transferred to a kneader and adjusted to a pH of 6.2 by adding 50% by weight sodium hydroxide solution.
  • the crushed gel is then dried in an air stream at 170 ° C., ground and sieved to a particle size distribution of 100-850 ⁇ m.
  • 1 kg of this product was sprayed in a ploughshare mixer with a solution of 2 g of RETEN 204 LS (polyamidoamine-epichlorohydrin adduct from Hercules), 30 g of deionized water and 30 g of 1,2-propanediol and then at 150 for 60 minutes ° C annealed.
  • RETEN 204 LS polyamidoamine-epichlorohydrin adduct from Hercules
  • a previously prepared separately, cooled to approx. 25 ° C and inerted by introducing nitrogen monomer solution is sucked into a laboratory kneader with a working volume of 2 1, which was absolutely evacuated by means of a vacuum pump to 980 mbar.
  • the monomer solution is composed as follows: 825.5 g demineralized water, 431 g acrylic acid, 335 g NaOH 50%, 4.5 g "ethoxylated trimethylolpropane triacrylate" (SR 9035 oligomer from SARTOMER) and 1.5 g pentaerythritol triallyl ether (P. -30 from Daiso).
  • the kneader is evacuated and then aerated with nitrogen.
  • the jacket heating circuit is switched back to bypass and polymerized for 15 minutes without heating / cooling, then cooled, the product is discharged, and the resulting gel particles are dried at temperatures above 100 ° C, ground and to a particle size distribution of 100 - sieved 850 ⁇ m.
  • 500 g of this product were sprayed in a ploughshare mixer with a solution of 2 g of 2-oxazolidinone, 25 g of deionized water and 10 g of 1,2-propanediol and then heat-treated at 185 ° C. for 70 minutes. The following properties were measured:
  • Free swell rate 0.56 g / gs
  • 3600 g of demineralized water and 1400 g of acrylic acid are placed in a polyethylene vessel with a capacity of 10 l, which is well insulated by foamed plastic material. Now 14 g of tetraallyl ammonium chloride are added.
  • the initiators consisting of 2.2 g of 2,2'-azobisamidino-propanedihydrochloride, dissolved in 20 g of deionized water, 4 g of potassium peroxodisulfate, dissolved in 150 g of deionized water and 0.4 g Ascorbic acid, dissolved in 20 g of demineralized water, added successively and stirred.
  • reaction solution is then left to stand without stirring, a solid gel being formed by the onset of polymerization, in the course of which the temperature rises to approximately 90 ° C. This is then crushed mechanically, adjusted to a pH of 6.0 by adding 50% by weight sodium hydroxide solution.
  • the gel is then dried, ground and sieved to a particle size distribution of 100-850 ⁇ m. 1 kg of this dried hydrogel is sprayed in a ploughshare mixer with a solution consisting of 40 g of deionized water, 40 g of i-propanol and 0.5 g of ethylene glycol diglycidyl ether and then heat-treated at 140 ° C. for 60 minutes.
  • the product described here has the following properties:
  • a previously prepared separately, cooled to approx. 25 ° C and inerted by introducing nitrogen monomer solution is sucked into a laboratory kneader with a working volume of 2 1, which was absolutely evacuated by means of a vacuum pump to 980 mbar.
  • the monomer solution is composed as follows: 825.5 g demineralized water, 431 g acrylic acid, 335 g NaOH 50%, 3.0 g methylenebisacrylamide.
  • the kneader is evacuated and then aerated with nitrogen. This process is repeated 3 times.
  • a jacket heating circuit (bypass) preheated to 75 ° C is switched to the kneader jacket, the stirrer speed is increased to 96 rpm.
  • the jacket heating circuit is switched back to bypass and polymerized for 15 minutes without heating / cooling, then cooled, the product is discharged, and the resulting gel particles are dried at temperatures above 100 ° C, ground and to a particle size distribution of 100 - sieved 850 ⁇ m. The following properties were measured:
  • the comminuted gel is then dried in an air stream at 170 ° C., ground, sieved to a particle size distribution of 100-850 ⁇ m and homogeneously mixed with 1.0% by weight of Aerosil 200 (pyrogenic silica, commercial product from Degussa AG, average primary particle size 12 nm ). 1 kg of this product was sprayed in a ploughshare mixer with a solution of 2 g of RETEN 204 LS (polyamidoamine-epichlorohydrin adduct from Hercules), 30 g of deionized water and 30 g of 1,2-propanediol and then at 150 for 60 minutes ° C annealed. The following properties were measured:
  • the initiators 6.0 g of 2,2'-azobisamidinopropane dihydrochloride, dissolved in 60 g of deionized water, 12 g of potassium peroxodisulfate, dissolved in 450 g of deionized water, and 1.2 g of ascorbic acid are dissolved at a temperature of 4.degree in 50 g of demineralized water, added in succession and stirred well.
  • the reaction solution is then left to stand without stirring, a gel being formed by the onset of polymerization, in the course of which the temperature rises to approximately 85.degree. This is then transferred to a kneader and adjusted to a pH of 6.2 by adding 50% by weight sodium hydroxide solution.
  • the comminuted gel is then dried in an air stream at 170 ° C., ground, and sieved to a particle size distribution of 100-850 ⁇ m.
  • 1 kg of this product was in a ploughshare mixer with a solution of 2 g of RETEN 204 LS (polyamidoamine-epichlorohydrin adduct from Hercules), 5 g of aluminum sulfate Al 2 (SO 4 ) 3 , 30 g of deionized water and 30 g of 1,2-propanediol are sprayed on and then annealed at 150 ° C. for 60 minutes. The following properties were measured:

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  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Hematology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
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Abstract

L'invention concerne des hydrogels non hydrosolubles, gonflant dans l'eau, revêtus de séparateurs stériques ou électrostatiques. Avant d'être revêtus, ces hydrogels présentent les caractéristiques suivantes: absorption sous pression (0,7 psi) d'au moins 20 g/g, module d'élasticité du gel d'au moins 1600 Pa. Les hydrogels revêtus présentent de préférence les caractéristiques suivantes : capacité de rétention après centrifugation d'au moins 14 g/g, perméabilité aux flux salins d'au moins 30 x 10<-7> cm<3> s/g et taux de gonflement libre d'au moins 0,15 g/g s et/ou durée maximale de vortex de 160 s.
EP01985933A 2000-12-29 2001-12-28 Hydrogels revetus de separateurs steriques ou electrostatiques Withdrawn EP1363682A1 (fr)

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DE10065251 2000-12-29
DE10065251 2000-12-29
PCT/EP2001/015376 WO2002053199A1 (fr) 2000-12-29 2001-12-28 Hydrogels revetus de separateurs steriques ou electrostatiques

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BR (1) BR0116621A (fr)
CA (1) CA2433044A1 (fr)
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MXPA03005787A (es) 2003-09-10
CN1482924A (zh) 2004-03-17
KR20030068198A (ko) 2003-08-19
CA2433044A1 (fr) 2002-07-11
JP2004517173A (ja) 2004-06-10
BR0116621A (pt) 2003-12-23
PL362772A1 (en) 2004-11-02

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