WO2014135364A1

WO2014135364A1 - Superabsorbent polymers with improved odour-control properties and method for the production thereof

Info

Publication number: WO2014135364A1
Application number: PCT/EP2014/053079
Authority: WO
Inventors: Christoph Loick; Anne Ix-Mund; Nicolaas De Bruin; Scott Smith
Original assignee: Evonik Industries Ag
Priority date: 2013-03-06
Filing date: 2014-02-18
Publication date: 2014-09-12
Also published as: DE102013203779A1; TW201434941A

Abstract

The invention relates to a water-absorbing polymer and to a method for the production thereof, comprising the method steps: (i) blending (α1) between 0.1 and 99.999 wt. %, preferably between 20 and 98.99 wt. % and especially preferably between 30 and 98.95 wt. % polymerizable, ethylenically unsaturated monomers containing acid groups or their salts, or polymerizable, ethylenically unsaturated monomers containing a protonated or quaternized nitrogen, or blends thereof, with blends having at least ethylenically unsaturated monomers which contain acid groups, preferably acrylic acid, being especially preferred; (α2) between 0 and 70 wt. %, preferably between 1 and 60 wt. % and especially preferably between 1 and 40 wt. % polymerized, ethylenically unsaturated monomers which can be copolymerized with the blends in (α1); (α3) between 0.001 and 10 wt. %, preferably between 0.01 and 7 wt. % and especially preferably between 0.05 and 5 wt. % one or more cross-linking agents; (α4) between 0 and 30 wt. %, preferably between 1 and 20 wt. % and especially preferably between 5 and 10 wt. % water-soluble polymers; (α5) between 0 and 20 wt. %, preferably between 2.5 and 15 wt. % and especially preferably between 5 and 10 wt. % water; in addition to (α6) between 0 and 20 wt. %, preferably between 0 and 10 wt. % and especially preferably between 0.1 and 8 wt. % one or more auxiliary agents, the total weight percentages (α1) to (α6) adding up to 100 wt. %; (ii) radical polymerization with cross-linking in order to form a water-insoluble, aqueous, untreated hydrogel-polymer; (iii) drying the hydrogel-polymer; (iv) milling and screening the water-absorbing polymer; (v) surface cross-linking the milled and screened hydrogel-polymer; and (vi) drying and making-up the water-absorbing polymer. Preferably between 0.07 and 7 wt. %, in relation to the acrylic acid, of a salt of an α,β-unsaturated carboxylic acid selected from the group comprising α,β-di-unsaturated carboxylic acids with a C₆- to C₁₄parent substance is added to the water-absorbing polymer. The invention also relates to a method for producing a hydrogel-polymer, to the product of said method and to the use of said polymer.

Description

Superabsorbent polymers with improved odor control properties and process for its preparation

The present invention relates to superabsorbent polymers having improved odor control properties and to processes for their preparation. DE 40 20 780 C1 discloses the post-treatment of superabsorbent polymers by post-crosslinking the surfaces of the polymer particles. By the post-crosslinking of the surface of the water-absorbing polymer particles, in particular, the absorption capacity of the polymer particles is increased under the action of pressures. DE 199 09 653 A1 and DE 199 09 838 A1 describe powdery, postcrosslinked, water, aqueous or serous liquids or blood absorbing polymers which are based on acid group-carrying monomers and which have been coated with a surface postcrosslinking agent and a cation in aqueous solution and postcrosslinked are. The polymers disclosed in this prior art have advantageous absorption properties, in particular high permeability, over conventional polymers.

In the longer wearing absorbent articles containing hygiene products, especially if they have already absorbed some body fluids such as urine, it may come due to the organic constituents of the urine and the body heat of the wearer soon to an unpleasant odor. In order to counteract this, numerous attempts have been made to obtain a binding of the odor-forming substances by appropriate additions to the components of the hygiene article which are different from the superabsorber, or to drown the odor by perfumes or the like. The introduction of such substances in the form of superabsorbers of various constituents often has a negative effect on the performance of these sanitary articles during wear. For example, the body fluids often contain the odor-inhibiting or odor-reducing substances initially present in the superabsorber area, for example, by flooding into a superabsorbent-containing area of a hygiene article, where they then have a negative effect on the performance of the superabsorber and thus of the hygiene article as a whole. Furthermore, on this Concept disadvantageous that the majority of the body fluid discharged into the sanitary article is anyway in the superabsorbent and therefore located outside of the superabsorbent odor-inhibiting or odor-reducing substances can develop their effect worse.

DE 198 25 486 and DE 199 39 662 A1 disclose the combination of superabsorbents with cyclodextrin for reducing odors. However, this quite promising approach suggests that only under certain conditions, namely when it is ensured that the cyclodextrin does not separate from the superabsorber, does the cyclodextrin exhibit its odor-inhibiting effect in the superabsorbent. Here it is preferred that the cyclodextrin is incorporated at least into the surface of the superabsorbent article by covalently and / or ionically bound and / or entrapped in cyclodextrin and / or cyclodextrin derivatives. DE 103 34 271 furthermore discloses superabsorbent agglomerates which can have a multiplicity of odor binders homogeneously in the agglomerate. However, this document, which discloses an excellent solution for the use of superabsorbent fine particles, does not provide any superabsorbents with odor-binding properties which are particularly suitable for use in hygiene articles. Thus, in addition to the efficient and effective use of the odor binders, the superabsorber properties influenced by this odor binder are in need of improvement.

DE-A-10 2005 055 497 teaches to provide superabsorbent polymers by contacting them with metal salts of ricinoleic acid and / or with amino acids having improved odor-binding properties.

In general, the present invention has the object to mitigate or even overcome the disadvantages resulting from the prior art. It was an object of the invention to provide a water-absorbing polymer which on the one hand has good odor-binding properties. On the other hand, it should be ensured that the performance of the hygiene article containing this odor-binding water-absorbing polymer is substantially equal to or even better than the performance of the hygiene article with a superabsorbent, which does not include the odor binder like the odor-binding water-absorbing polymer. In particular, the performance properties of the water-absorbing polymer should be improved by the use of odor-binding additives, which are as small as possible should be used, possibly not at all or at most be slightly influenced. Advantageously, the performance properties of the water-absorbing polymer should even be improved by the addition of the odor-controlling additive. Furthermore, the water-absorbing polymer should, if it comes into contact with aqueous body fluids, in particular with urine or iron-containing liquids, such as, for example, blood or menstrual fluid, preferably should not be prone to excessive discoloration. Furthermore, it was an object of the invention to provide a method by which such a water-absorbing polymer can be obtained. In addition, it was an object of the invention to provide a hygiene article which, in addition to good odor-binding properties, also exhibits good performance. In addition, the present invention has for its object to provide water-absorbing polymers that can generally be incorporated into networks or can be found as a composite or as such use in chemical products or their components.

These objects are achieved by the subject matter of the categorizing claims. Advantageous embodiments and further developments, which may occur individually or in combination, are the subject of the respective dependent claims.

A contribution to the solution of the aforementioned object is afforded by a water-absorbing polymer according to the invention based on:

(a1) 20-99.999 wt .-%, preferably 55-98.99 wt .-% and particularly preferably 70- 98.79 wt .-% of polymerized, ethylenically unsaturated, acid group-carrying monomers or their salts or polymerized, ethylenically unsaturated, one protonated or quaternized nitrogen-containing monomers, or mixtures thereof, wherein at least ethylenically unsaturated, acid group-containing monomers, preferably acrylic acid-containing mixtures are particularly preferred,

(a2) 0-80 wt .-%, preferably 0-44.99 wt .-% and particularly preferably 0.1 -

44.89% by weight of polymerized, monoethylenically unsaturated monomers copolymerizable with (a1),

(a3) 0.001-5 wt .-%, preferably 0.01 -3 wt .-% and particularly preferably 0.01 -

2.5% by weight of one or more crosslinkers,

(a4) 0-30% by weight, preferably 0-5% by weight and particularly preferably 0.1-5% by weight of a water-soluble polymer, (α5) 0-20 wt .-%, preferably 2.5-15 wt .-% and particularly preferably 5-10 wt .-% water, and

(a6) 0-20 wt .-%, preferably 0-10 wt .-% and particularly preferably 0, 1-8 wt .-% of one or more auxiliaries, wherein the sum of the amounts by weight of (a1) to (a6) 100 wt .-%,

in which

the water-absorbing polymer 0.01 to 10 wt .-%, preferably 0.02 to 8 wt .-% and particularly preferably 0.07 to 7 wt .-% of a salt of an α, β-diunsaturated carboxylic acid, based on the acrylic acid , contains.

Preferably, 0.01 to 1 wt .-% of a salt of an α, β-double unsaturated carboxylic acid, based on the acrylic acid used. It may be advantageous if in addition to the salt of an α, β-diunsaturated carboxylic acid and free α, β-diunsaturated carboxylic acid is present. Preferably, the free α, β-diunsaturated carboxylic acid is identical to the α, β-diunsaturated carboxylic acid, the salt of which is used.

Particular preference is given to using α, β-doubly unsaturated carboxylic acids or their salts with a C5- to C-1 basic body.

By the term "α, β-diunsaturated carboxylic acid having a C5 to C14

For the purposes of the present invention, the term "basic body" refers to acids from the group of hexadienoic acid, heptadiene, octadiene, nonadiene, decadiene, unodecadiene, dodecadiene, tridecadiene, or tetradecadienoic acid or their isomers or stereoisomers Also understood as meaning compounds having two or more functional groups which can coordinate to a monovalent, bivalent or polyvalent metal cation Within the scope of the present invention, substituents from the group of the halides, amines, esters, carboxylates, imines are used as functional groups , Understood.

The salts are metals derived from the group of alkali, alkaline earth and boron groups. Here, preference is given to the metals from the group of sodium, potassium, cesium, rubidium, magnesium, calcium, strontium, barium, aluminum, gallium, indium. Particular preference is given to those from the group of sodium, potassium, calcium, magnesium, if appropriate mixtures thereof. Particularly preferred are metals from the group of sodium, potassium, calcium and magnesium. In a further embodiment, the water-absorbing polymer comprises at least one salt from the group of α, β-diunsaturated carboxylic acids with C5 to C14

Basic body from the group of hexadienoic acid, heptadiene, octadiene, nonadiene, decadiene, unodecadiene, dodecadiene, tridecadiene, - or tetradecadienoic acid or their isomers or stereoisomers.

In a particularly preferred embodiment, the α, β-diunsaturated carboxylic acid is sorbic acid.

In a further embodiment, the water-absorbing polymer contains at least one salt from the group of α, β-diunsaturated carboxylic acids with a C5 bis

C-14 base and a counterion from the group of sodium, potassium, magnesium,

Calcium, strontium, barium, or aluminum.

In this case, preferred water-absorbing polymer structures according to the invention are in particular fibers, foams or particles, with fibers and particles being particularly preferred and particles being most preferred.

According to preferred polymer fibers are dimensioned so that they can be incorporated into or as yarn for textiles and also directly in textiles. It is preferred according to the invention that the polymer fibers have a length in the range of 1 to 500 mm, preferably 2 to 500 mm and more preferably 5 to 100 mm and a diameter in the range of 1 to 200 denier, preferably 3 to 100 denier and more preferably 5 own up to 60 deniers.

Polymer particles preferred according to the invention are dimensioned such that they have an average particle size according to ERT 420.2-02 in the range of 10 to 3000 μm, preferably 20 to 2000 μm and particularly preferably 150 to 850 μm or 150 to 600 μm. It is particularly preferred that the proportion of the polymer particles having a particle size in a range of 300 to 600 μηη at least 30 wt .-%, more preferably at least 40 wt .-%, more preferably at least 50 wt .-% and most preferably at least 75% by weight, based on the total weight of the water-absorbing polymer particles. According to another embodiment of the water-absorbing polymer structures according to the invention, the proportion of polymer particles having a particle size in a range from 150 to 850 μm is at least 50% by weight, particularly preferably at least 75% by weight, moreover preferred at least 90% by weight, and most preferably at least 95% by weight, based on the total weight of the water-absorbing polymer particles.

The monoethylenically unsaturated acid group-containing monomers (a1) may be partially or completely, preferably partially neutralized. The monoethylenically unsaturated monomers containing acid groups are preferably neutralized to at least 10 mol%, particularly preferably to at least 25 to 50 mol% and moreover preferably to 50-90 mol%. The neutralization of the monomers (a1) can take place before, but also after the polymerization. In this case, the partial neutralization takes place to at least 10 mol%, more preferably at least 25 to 50 mol% and more preferably to 50-90 mol%. Furthermore, the neutralization can be carried out with alkali metal hydroxides, alkaline earth metal hydroxides, ammonia and carbonates and bicarbonates. In addition, every other base is conceivable, which forms a water-soluble salt with the acid. Also a mixed neutralization with different bases is conceivable. Preference is given to neutralization with ammonia or with alkali metal hydroxides, particularly preferably with sodium hydroxide or with ammonia.

Furthermore, in the case of a polymer, the free acid groups may predominate, so that this polymer has a pH lying in the acidic range. This acidic water-absorbing polymer may be at least partially neutralized by a polymer having free basic groups, preferably amine groups, which is basic as compared to the acidic polymer. These polymers are referred to in the literature as Mixed-Bed Ion-Exchange Absorbent Polymers (MBIEA polymers) and are disclosed inter alia in WO 99/34843 The disclosure of WO 99/34843 is hereby incorporated by reference and thus applies As a general rule, MBIEA polymers are a composition comprising, on the one hand, basic polymers capable of exchanging anions and, on the other hand, cations which are acidic in comparison to the basic polymer The basic polymer has basic groups and is typically obtained by the polymerization of monomers bearing basic groups or groups which can be converted to basic groups , secondary or tertiary amines or the corresponding phosphines or at least two of the above functional groups of monomers include, in particular, ethyleneamine, allylamine, diallylamine, 4-aminobutene, alkyloxycycline, vinylformamide, 5-aminopentene, carbodiimide, formaldacin, melamine and the like, and their secondary or tertiary amine derivatives. Preferred monoethylenically unsaturated acid group-containing monomers (a1) are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, β-methylacrylic acid (crotonic acid), α-phenylacrylic acid, β-acryloxypropionic acid, sorbic acid, α-chlorosorbic acid, 2'-methylisocrotonic acid, Cinnamic acid, p-chlorocinnamic acid, .beta.-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene and maleic anhydride, with acrylic acid and methacrylic acid being particularly preferred, and acrylic acid being moreover preferred.

In addition to these carboxylate-containing monomers, preferred monoethylenically unsaturated acid group-containing monomers (a1) are ethylenically unsaturated sulfonic acid monomers or ethylenically unsaturated phosphonic acid monomers.

Preferred ethylenically unsaturated sulfonic acid monomers are allylsulfonic acid or aliphatic or aromatic vinylsulfonic acids or acrylic or methacrylic sulfonic acids. As aliphatic or aromatic vinylsulfonic acids, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinyltoluenesulfonic acid and styrenesulfonic acid are preferred. As acrylic or methacrylic sulfonic acids, preference is given to sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxy-3-methacryloxypropylsulfonic acid and (meth) acrylamidoalkylsulfonic acids, such as 2-acrylamido-2-methylpropanesulfonic acid.

Preferred ethylenically unsaturated phosphonic acid monomers are vinylphosphonic acid, allylphosphonic acid, vinylbenzylphosphonic acid, (meth) acrylamidoalkylphosphonic acids, acrylamidoalkyldiphosphonic acids, phosponomethylated vinylamines and (meth) acrylicphosphonic acid derivatives.

As ethylenically unsaturated, a protonated nitrogen-containing monomers (a1) are preferably dialkylaminoalkyl (meth) acrylates in protonated form, for example dimethylaminoethyl (meth) acrylate hydrochloride or dimethylaminoethyl (meth) acrylate hydrosulfate, and dialkylaminoalkyl (meth) acrylamides in protonated form, for example, dimethylaminoethyl (meth) acrylamide hydrochloride, diemethylaminopropyl (meth) acrylamide hydrochloride, dimethylaminopropyl (meth) acrylamide hydrosulfate or dimethylaminoethyl (meth) acrylamide hydrosulfate.

Ethylenically unsaturated monomers (a1) containing a quaternized nitrogen are dialkylammoniumalkyl (meth) acrylates in quaternized form, for example trimethylammonium methyl (meth) acrylate methosulfate or dimethylethylammoniumethyl (meth) acrylate-ethylene sulfate and (meth) acrylamido-alkyldialkylamines in quaternized form, for example (meth) acrylamidopropyltrimethylammonium chloride, trimethylammoniumethyl (meth) acrylate chloride or (meth) acrylamidopropyltrimethylammonium sulfate. As monoethylenically unsaturated monomers (a2) which can be copolymerized with (a1), preference is given to acrylamides and methacrylamides.

Preferred (meth) acrylamides are acrylamide and methacrylamide alkyl-substituted (meth) acrylamides or aminoalkyl-substituted derivatives of (meth) acrylamide, such as N-methylol (meth) acrylamide, N, N-dimethylamino (meth) acrylamide, dimethyl (meth) acrylamide or Diethyl (meth) acrylamide Possible vinylamides are, for example, N-vinylamide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, vinylpyrrolidone. Particularly preferred among these monomers is acrylamide. Further, as the monoethylenically unsaturated monomers (a2) copolymerizable with (a1), water-dispersible monomers are preferable. As the water-dispersible monomers, preferred are acrylic acid esters and methacrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate or butyl (meth) acrylate, and vinyl acetate, styrene and isobutylene.

Crosslinkers (a3) preferred according to the invention are compounds which have at least two ethylenically unsaturated groups within a molecule (crosslinker class I), compounds which have at least two functional groups which react with functional groups of the monomers (a1) or (a2) in a condensation reaction ( = Condensation crosslinker), in an addition reaction or in a ring-opening reaction (crosslinker class II), compounds containing at least one ethylenically unsaturated group and at least one functional group functionalized with groups of monomers (a1) or (a2) in a condensation reaction, in can react an addition reaction or in a ring-opening reaction (crosslinker III), or polyvalent metal cations (crosslinker class IV). Crosslinking of the polymers by the free radical polymerization of the ethylenically unsaturated groups of the crosslinker molecule with the monoethylenically unsaturated monomers (a1) or (a2) is achieved by the compounds of crosslinker class I, while in the compounds of crosslinker class II and the polyvalent metal cations of crosslinker class IV a crosslinking of the polymers by condensation reaction of the functional groups (crosslinker class II) or by electrostatic interaction of the polyvalent metal cation (crosslinker class IV) with the functional groups of the monomers (a1) or (α2) is reached. In the case of the compounds of the crosslinker class III, crosslinking of the polymer accordingly takes place both by free-radical polymerization of the ethylenically unsaturated group and by condensation reaction between the functional group of the crosslinker and the functional groups of the monomers (a1) or (a2).

Preferred compounds of crosslinker class I are poly (meth) acrylates which are obtained, for example, by the reaction of a polyol such as, for example, ethylene glycol, propylene glycol, trimethylolpropane, 1,6-hexanediol, glycerol, pentaerythritol, polyethylene glycol or polypropylene glycol, an aminoalcohol, a polyalkylenepolyamine, such as Diethylenetriamine or triethylenetetraamine, or an alkoxylated polyol can be recovered with acrylic acid or methacrylic acid. Further preferred compounds of crosslinker class I are polyvinyl compounds, poly (meth) allyl compounds, (meth) acrylic esters of a monovinyl compound or (meth) acrylic acid esters of a mono (meth) allyl compound, preferably of the mono (meth) allyl compounds of a polyol or of an aminoalcohol , In this context, reference is made to DE 195 43 366 and DE 195 43 368. The disclosures are hereby incorporated by reference and thus are considered part of the disclosure.

Examples of compounds of crosslinker class I are alkenyldi (meth) acrylates, for example ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,3-butylene glycol di ( meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,18-octadecanediol di (meth) acrylate, cyclopentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, methylenedi (meth) acrylate or pentaerythritol di (meth) acrylate, alkenyldi (meth) acrylamides, for example N-methyldi (meth) acrylamide, N, N'-3-methylbutylidenebis (meth) acrylamide, N, N '- (1, 2-dihydroxyethylene) bis (meth) acrylamide, N, N'-hexamethylene bis (meth) acrylacrylamide or Ν, Ν'-methylenebis (meth) acrylamide, polyalkoxydi (meth) acrylates, for example diethylene glycol diol - (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate or tetrapropylene glycol di (meth) acrylate , Bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, benzylidinedi (meth) acrylate, 1, 3-di (meth) acryloyloxypropanol-2, hydroquinone di (meth) acrylate, Di (meth) acrylate ester of preferably oxyalkylated, preferably ethoxylated trimethylolpropane, thioethylene glycol di (meth) acrylate, thiopropylene glycol di (meth) acrylate, thiopolyethylene glycol di (meth) acrylate, thiopolypropylene glycol di (meth) acrylate, divinyl ether, preferably with 1 to 30 moles of alkylene oxide per hydroxyl group, for example, 1,4-butanediol divinyl ether, divinyl esters, for example divinyl adipate, alkadienes, for example butadiene or 1,6-hexadiene, divinylbenzene, di (meth) allyl compounds, for example di (meth) allyl phthalate or di (meth) allyl succinate, homopolymers and copolymers of di (meth) allyldimethylammonium chloride and homopolymers and copolymers of diethyl (meth) allylaminomethyl (meth) acrylate ammonium chloride, vinyl (meth) acryl compounds, for example vinyl (meth) acrylate, (meth) allyl (meth) acryl compounds, for example (meth) allyl (meth) acrylate, with 1 to 30 moles of ethylene oxide per hydroxyl ethoxylated (meth) allyl (meth) acrylate, di (meth) allyl ester of polycarboxylic acids, for example di (meth) allyl maleate, di (meth) allyfumarate, di (meth) allyl succinate or di (meth) allyl terephthalate, compounds having 3 or more ethylenically unsaturated, radically polymerizable groups, for example glycerol tri (meth) acrylate, (meth) acrylate ester of preferably with 1 to 30 moles of ethylene oxide per hydroxyl group oxyethylated glycerol, trimethylolpropane tri (meth) acrylate, tri (meth) acrylate ester of preferably with 1 to 30 moles of alkylene oxide per hydroxyl group oxyalkylated, preferably ethoxylated trimethylolprop pans, trimethacrylamide, (meth) allylidenedi (meth) acrylate, 3-allyloxy-1,2-propanediol di (meth) acrylate, tri (meth) allyl cyanurate, tri (meth) allyl isocyanurate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri ( meth) acrylate, (meth) acrylic acid ester of preferably with 1 to 30 moles of ethylene oxide per hydroxyl group oxyethylated pentaerythritol, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Trivinyltrimelli- tat, tri (meth) allylamine, di (meth) allylalkylamine, for example Di (meth) allylmethylamine, tri (meth) allyl phosphate, tetra (meth) allylethylenediamine, poly (meth) allyl esters, tetra (meth) allyloximethane or tetra (meth) allylammonium halides.

Preferred compounds of crosslinker class II are compounds which have at least two functional groups which are preferred in a condensation reaction (= condensation initiator), in an addition reaction or in a ring-opening reaction with the functional groups of the monomers (a1) or (a2) with acid groups that can react monomers (a1). These functional groups of the compounds of crosslinker class II are preferably alcohol, amine, aldehyde, glycidyl, isocyanate, carbonate or epichloro functions.

Examples of compounds of crosslinker class II are polyols, for example ethylene glycol, polyethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, propylene glycol, polypropylene glycols such as dipropylene glycol, tripropylene glycol or tetrapropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 2,5-hexanediol, glycerol, polyglycerol, trimethylolpropane, polyoxypropylene, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, pentaerythritol, polyvinyl alcohol and sorbitol, amino alcohols, for example ethanolamine, diethanolamine , Triethanolamine or propanolamine, polyamine compounds, for example, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine or pentaethylenehexaamine, polyglycidyl ether compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, Glycerinpolyglycidy- ether, Pentareritritpolyglycidylether, propylene glycol Polypropylenglykoldiglyci- dylether, neopentyl glycol diglycidyl ether, Hexandiolglycidylether, Trimethylolpropanpolyglyci- dylether, sorbitol, Phtahlsäurediglycidylester, adipic acid diglycidyl ester, 1, 4-phenylene-bis (2- oxazoline), glycidol, polyisocyanates, preferably diisocyanates such as 2,4-toluenediisocyanate and hexamethylene diisocyanate, polyaziridine compounds such as 2,2-bis-hydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethyleneurea and diphenylmethane bis- 4,4 ^'-N, ^N' -diethylenharnstoff, Halogenperoxide example epichloro- and epibromohydrin and α-methylepichlorohydrin, alkylene carbonates such as 1, 3-dioxolan-2-one (ethylene carbonate), 4-methyl-1, 3-dioxolan-2- on (propylene carbonate), 4,5-dimethyl-1,3-d ioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1, 3-dioxan-2-one, 4-methyl-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, poly-1,3-dioxolane-2 on, polyquartare amines such as condensation products of dimethylamines and epichlorohydrin. Further preferred compounds of crosslinker class II are polyoxazolines such as 1,2-ethylenebisoxazoline, crosslinkers with silane groups such as .gamma.-glycidoxypropyltrimethoxysilane and .gamma.-aminopropyltrimethoxysilane, oxazolidinones such as 2-oxazolidinone, bis- and poly-2-oxazolidinones and diglycol silicates.

As compounds of class III are hydroxyl- or amino-containing esters of (meth) acrylic acid, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate and hydroxyl- or amino-containing (meth) acrylamides or mono (meth) allyl compounds of diols preferred.

The polyvalent metal cations of crosslinker class IV are preferably derived from mono- or polyvalent cations, the monovalent particular of alkali metals such as potassium, sodium, lithium, with lithium being preferred. Preferred divalent cations are derived from zinc, beryllium, alkaline earth metals such as magnesium, calcium, strontium, with magnesium being preferred. Further higher-grade cations which can be used according to the invention are cations of aluminum, iron, chromium, manganese, titanium, zirconium and other transition metals, as well as double salts of such cations or mixtures of the abovementioned salts. Preference is given to aluminum salts and alums and their different hydrates such. B. AICI3 x 6H ₂ 0, NaAl (S0 ₄ ) ₂ * 12 H ₂ 0, KAI (S0 ₄ ) ₂ * 12 H ₂ 0 or AI ₂ (S0 ₄ ) ₃ x14-18 H ₂ 0 used. Al ₂ (SO ₄ ) ₃ and its hydrates are particularly preferably used as crosslinker of crosslinking class IV. The superabsorbent particles used in the process according to the invention are preferably crosslinked by crosslinkers of the following crosslinker classes or by crosslinkers of the following combinations of crosslinker classes: I, II, III, IV, II, III, IV, II, III, III, III IV, II III IV, II IV or III IV. The above combinations of crosslinker classes each represent a preferred embodiment of crosslinkers of a superabsorbent particle used in the process according to the invention.

Further preferred embodiments of the superabsorbent particles used in the process according to the invention are polymers which are crosslinked by means of any of the abovementioned crosslinkers of crosslinker class I. Among them, water-soluble crosslinkers are preferred. In this context, N, N ^{'methylenebisacrylamide,} polyethylene glycol di (meth) acrylates, triallylmethylammonium chloride, Tetraallylammoniumchlo- chloride and with 9 moles of ethylene oxide per mole of acrylic acid produced Allylnonaethylen- glykolacrylat particularly preferred.

As water-soluble polymers (a4), water-soluble polymers such as partially or fully saponified polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivatives, polyglycols or polyacrylic acid may be present in the SAP particles, preferably in copolymerized form. The molecular weight of these polymers is not critical as long as they are water-soluble. Preferred water-soluble polymers are starch or starch derivatives or polyvinyl alcohol. The water-soluble polymers, preferably synthetic, such as polyvinyl alcohol, can also serve as a grafting base for the monomers to be polymerized.

As auxiliaries (a5), in the polymers, organic or inorganic particles such as odor binders, in particular zeolites or cyclodextrins, skin care substances, surface-active agents or antioxidants are included.

The preferred organic excipients include cyclodextrins or their derivatives and polysaccharides. In addition, cellulose and cellulose derivatives such as CMC, cellulose ethers are preferred. Preferred cyclodextrins or cyclodextrin derivatives are those compounds which are disclosed in DE-A-198 25 486 on page 3, line 51 to page 4, line 61. The aforementioned section of this published patent application is hereby incorporated by reference and is considered part of the disclosure of the present invention. Particularly preferred cyclodextrins are non-derivatized α-, β-, γ- or δ-cyclodextrins. As inorganic particulate adjuvants, it is possible to use all materials which are customarily used for modifying the properties of water-absorbing polymers. The preferred inorganic auxiliaries include sulfates such as Na ₂ SO ₄ , lactates such as sodium lactate, silicates, in particular skeletal silicates such as zeolites or silicates obtained by drying aqueous silica solutions or silica sols, for example the commercially available products such as precipitated silicas and fumed silicas, for example aerosils having a particle size in the range of 5 to 50 nm, preferably in the range of 8 to 20 nm, such as "Aerosil 200" from Evonik Industries AG, aluminates, titanium dioxides, zinc oxides, clay materials and other minerals familiar to the person skilled in the art, and also carbonaceous inorganic materials.

Preferred silicates are all natural or synthetic silicates described in Hollemann and Wiberg, Lehrbuch der Anorganischen Chemie, Walter de Gruyter-Verlag, 91.-100. Edition, 1985 on pages 750 to 783, as silicates are disclosed. The foregoing section of this textbook is hereby incorporated by reference and is considered part of the disclosure of the present invention.

Particularly preferred silicates are the zeolites. As zeolites, it is possible to use all synthetic or natural zeolites known to the person skilled in the art. Preferred natural zeolites are zeolites of the natrolite group, the harmotome group, the mordenite group, the chabazite group, the faujasite group (sodalite group) or the analcite group. Examples of natural zeolites are Analcim, Leucite, Pollucite, Wairakite, Bellbergite, Bikitaite, Boggsite, Brewsterite, Chabazite, Willhendersonite, Cowlesite, Dachiardite, Edingtonite, Epistilbit, Erionite, Faujasite, Ferrierite, Amicite, Garronite, Gismondine, Gobbinsite, Gmelinite, Gonnardite , Goosecreekite, Harmotom, Phillipsite, Wellsite, Clinoptilolite, Heulandite, Laumontite, Levyne, Mazzite, Merlinoite, Montesommaite, Mordenite, Mesolite, Natrolite, Scolecite, Offretite, Paranatrolite, Paulingite, Perlialite, Barrerite, Stilbite, Stellerite, Thomsonite, Chernichite or Yugawaralite , Preferred synthetic zeolites are zeolite A, zeolite X, zeolite Y, zeolite P or the product ABSCENTS®.

As zeolites, zeolites of the so-called "middle" type can be used, in which the Si0 ₂ / Al0 ₂ ratio is less than 10, particularly preferably the Si0 ₂ / Al0 ₂ - ratio of these zeolites in a range of 2 to 10. In addition to these "middle" zeolites, "high" type zeolites may also be employed, including, for example, the well-known "molecular sieve" zeolites of the ZSM and β-zeolite type, these "high" zeolites being preferably a SiO ₂ / AlO ₂ Ratio of at least 35, especially preferably characterized by a Si0 ₂ / Al0 ₂ ratio in a range of 200 to 500.

The aluminates used are preferably naturally occurring spinels, in particular ordinary spinel, zinc spinel, iron spinel or chromium spinel.

Preferred titanium dioxide is the pure titanium dioxide in the rutile, anatase and brookite crystal forms, as well as iron-containing titanium dioxides such as ilmenite, calcium-containing titanium dioxides such as titanite or perovskite.

Preferred clay materials are those described in Hollemann and Wiberg, Lehrbuch der Inorganischen Chemie, Walter de Gruyter-Verlag, 91.-100. Edition, 1985 pages 783 to 785, are disclosed as clay materials. The above section of this textbook is hereby incorporated by reference and is considered part of the disclosure of the present invention. Particularly preferred clay materials are kaolinite, lllite, halloysite, montmorillonite and talc.

Furthermore, as inorganic fine particles, the metal salts of mono-, oligo- and polyphosphoric acids are preferred according to the invention. Of these, in particular the hydrates are preferred, with the mono- to deca-hydrates and tri-hydrates being particularly preferred. Suitable metals are, in particular, alkali metals and alkaline earth metals, the alkaline earth metals being preferred. Among them, Mg and Ca are preferable, and Mg is particularly preferable. In connection with phosphates, phosphoric acids and their metal compounds is on Hollemann and Wiberg, Textbook of Inorganic Chemistry, Walter de Gruyter-Verlag, 91.-100. Edition, 1985, on pages 651-669. The foregoing section of this textbook is hereby incorporated by reference and is considered part of the disclosure of the present invention.

Preferred carbonaceous but not organic auxiliaries are those pure carbons which are described in Hollemann and Wiberg, Lehrbuch der Anorganischen Chemie, Walter de Gruyter-Verlag, 91.-100. Edition, 1985 on pages 705 to 708 are called Graphite. The foregoing section of this textbook is hereby incorporated by reference and is considered part of the disclosure of the present invention. Particularly preferred graphites are artificial graphites such as coke, pyrographite, activated carbon or carbon black. The water-absorbing polymers obtained in the process according to the invention are preferably obtainable by first producing a hydrogel polymer (VP) in particulate form from the abovementioned monomers and crosslinkers. The preparation of this starting material for the water-absorbing polymers is carried out, for example, by bulk polymerization, which preferably takes place in kneading reactors such as extruders, solution polymerization, spray polymerization, inverse emulsion polymerization or inverse suspension polymerization. The solution polymerization is preferably carried out in water as solvent. The solution polymerization can be continuous or discontinuous. From the prior art, a wide range of possible variations in terms of reaction conditions such as temperatures, type and amount of initiators and the reaction solution can be found. Typical processes are described in the following patents: US 4,286,082, DE 27 06 135, US 4,076,663, DE 35 03 458, DE 40 20 780, DE 42 44 548, DE 43 23 001, DE 43 33 056, DE 44 18 818. The disclosures are hereby incorporated by reference and thus are considered part of the disclosure.

As initiators for the initiation of the polymerization, it is possible to use all initiators which form free radicals under the polymerization conditions and which are customarily used in the production of superabsorbers. These include thermal initiators, redox initiators and photoinitiators whose activation is effected by high-energy radiation. The polymerization initiators may be dissolved or dispersed in a solution of monomers according to the invention. The use of water-soluble initiators is preferred. Suitable thermal initiators are all compounds known to the person skilled in the art and decomposing into free radicals under the influence of temperature. Particular preference is given here to thermal polymerization initiators having a half-life of less than 10 seconds, moreover preferably less than 5 seconds at less than 180 ° C., more preferably less than 140 ° C. Peroxides, hydroperoxides, hydrogen peroxide, persulfates and azo compounds are particularly preferred thermal polymerization initiators. In some cases it is advantageous to use mixtures of different thermal polymerization initiators. Among these mixtures, those of hydrogen peroxide and sodium or potassium peroxodisulfate are preferred, which can be used in any conceivable quantitative ratio. Suitable organic peroxides are preferably acetylacetone peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, capric peroxide, isopropyl peroxydicarbonate, 2-ethylhexyl peroxydicarbonate, t-butyl hydroperoxide, cumene hydroperoxide, t-amyl perpivalate, t-butyl Butylperpivalate, t-butylperneohexonate, t-butylisobutyrate, t-butylper-2-ethylhexenoate, t-butyl perisononanoate, t-butylpermaleate, t-butylperbenzoate, t-butyl-3,5,5-tri-methylhexanoate and amylperneodecanoate. Additionally preferred as the thermal polymerization initiators are: azo compounds such as Azobisisobutyronitrol, azobisdimethylvaleronitrile, 2,2 - azobis (2-amidinopropane) dihydrochloride, azo-bis-amidinopropane dihydrochloride, ^2,2'-azobis N-dimethylene (N, ) isobutyramidine dihydrochloride, 2- (carbamoylazo) - isobutyronitrile and 4,4 ^'- azobis (4-cyanovaleric acid). The compounds mentioned are used in conventional amounts, preferably in a range from 0.01 to 5, preferably from 0.1 to 2 mol%, in each case based on the amount of the monomers to be polymerized.

The redox initiators contain as oxidic component at least one of the abovementioned per compounds and as reducing component preferably ascorbic acid, glucose, sorbose, manose, ammonium or alkali metal hydrogen sulphite, sulphate, thiosulphate, hyposulphite or sulphide, metal salts such as iron II ions or silver ions or sodium hydroxymethylsulfoxylate. Preferably, ascorbic acid or sodium pyrosulfite is used as the reducing component of the redox initiator. Relative to the employed in the polymerization amount of monomers x10 ^"5 and 1 mol% of the reducing component of the redox initiator and 1 ^{x10" 5} to 5 mol% of the oxidizing component of the redox initiator used. 1 Instead of or in addition to the oxidizing component of the redox initiator, one or more, preferably water-soluble, azo compounds can be used.

When the polymerization is triggered by the action of high-energy radiation, so-called photoinitiators are usually used as the initiator. These may be, for example, so-called a-splitters, H-abstracting systems or even 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 their derivatives, azo compounds such as the abovementioned radical formers, substituted hexaarylbisimidazoles or acylphosphine oxides. Examples of azides are: 2- (N, N-dimethylamino) ethyl-4-azidocinnamate, 2- (N, N-dimethylamino) ethyl-4-azidonaphthyl ketone, 2- (N, N-dimethylamino) ethyl-4 -azidobenzoate, 5-azido-1-naphthyl-2 '- (N, N-dimethylamino) ethylsulfone, N- (4-sulfonylazidophenyl) maleimide, N-acetyl-4-sulfonylazidoaniline, 4-sulfonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide, p-azidobenzoic acid, 2,6-bis (p-azidobenzylidene) cyclohexanone and 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone. The photoinitiators, if used, are usually used in amounts of 0.01 to 5 wt .-%, based on the monomers to be polymerized. According to the invention, preference is given to using an initiator system consisting of hydrogen peroxide, sodium peroxodisulfate and ascorbic acid. In general, the polymerization is initiated with the initiators in a temperature range from 0 ° C to 90 ° C.

The polymerization reaction may be initiated by one initiator or by several co-acting initiators. Furthermore, the polymerization can be carried out in such a way that one first adds one or more redox initiators. In the further course of polymerization, thermal initiators or photoinitiators are then additionally applied, wherein in the case of photoinitiators the polymerization reaction is then initiated by the action of high-energy radiation. The reverse order, ie the initial initiation of the reaction by means of high-energy radiation and photoinitiators or thermal initiators, and initiation of the polymerization by means of one or more redox initiators taking place in the further course of polymerization is also conceivable.

In order to convert the resulting hydrogel polymers (VP) into a particulate form, these can, after their separation from the reaction mixture, first at a temperature in a range of 20 to 300 ° C, preferably in a range of 50 to 250 ° C and more preferably in a range of 100 to 200 ° C to a water content of less than 40 wt .-%, preferably less than 20 wt .-% and more preferably less than 10 wt .-%, each based on the total weight of the hydrogel polymer (VP). Drying is preferably carried out in ovens or dryers known to those skilled in the art, for example in belt dryers, tray dryers, rotary kilns, fluid bed dryers, plate dryers, paddle dryers or infrared dryers.

According to the present invention, the comminution is preferably carried out by dry milling, preferably by dry milling in a hammer mill, a pin mill, a ball mill or a roller mill. In a further embodiment of the present invention, the comminution of the hydrogel polymer can also be effected by the combinations of several of the above-described mills.

In a preferred embodiment of the process according to the invention, particles which have an inner region and a surface region bounding the inner region are obtained as water-absorbing polymers. Wherein the surface area has a different chemical composition than the interior area or in one physical property is different from the interior. Physical properties in which the interior differs from the surface area are, for example, the charge density or the degree of crosslinking. These water-absorbing polymers having an inner region and an inner region-limiting surface area are preferably obtainable by postcrosslinking near-surface, reactive groups of the particles of the hydrogel polymer (VP). This postcrosslinking can be effected thermally, photochemically or chemically.

Preferred crosslinking agents are the compounds of crosslinker class II and IV mentioned in connection with the crosslinkers (a3).

Diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, polyglycerol, propylene glycol, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, trimethylolpropane, pentaerythritol, polyvinyl alcohol, sorbitol, 1, 3 are particularly preferred among these compounds as secondary crosslinkers. Dioxolan-2-one (ethylene carbonate), 4-methyl-1,3-dioxolan-2-one (propylene carbonate), 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1, 3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 4-methyl- 1, 3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, 1,3-dioxolan-2-one, poly-1,3-dioxolan-2-one.

Ethylene carbonate is particularly preferably used as postcrosslinker. Preferred embodiments of the water-absorbing polymers are those which are postcrosslinked by crosslinkers of the following crosslinker classes or by crosslinkers of the following combinations of crosslinker classes: II, IV and II IV.

Preferably, the postcrosslinker is used in an amount ranging from 0.01 to 30% by weight, more preferably in an amount ranging from 0.1 to 20% by weight, and more preferably in an amount within a range of 0.3 to 5 wt .-%, each based on the weight of the superabsorbent polymers used in the post-crosslinking.

It is also preferred that postcrosslinking be effected by using a solvent comprising, preferably, water, water miscible organic solvents such as methanol or ethanol, or mixtures of at least two thereof, and the like Postcrosslinkers with the outside of the hydrogel polymer particles at a temperature in a range of 30 to 300 ^° C, more preferably in a range of 100 to 200 ^° C are brought into contact. The bringing into contact is preferably effected by spraying, the mixture consisting of postcrosslinker and solvent, on the hydrogel polymer particles and subsequent mixing of the hydrogel polymer particles brought into contact with the mixture. In this case, the postcrosslinker in the mixture is preferably in an amount in a range of 0.01 to 20 wt .-%, particularly preferably in an amount in a range of 0.1 to 10 wt .-%, based on the total weight of the mixture , contain. It is further preferred that in an amount in a range of 0.01 to 50 wt .-%, particularly preferably in an amount in a range of 0.1 to 30 wt .-%, each based on the weight of the hydrogel Polymer particles, is brought into contact with the hydrogel polymer particles.

Suitable condensation reactions are preferably the formation of ester, amide, imide or urethane bonds, the formation of ester bond being preferred.

In addition, other additives and effect substances can be added to the hydrogel polymers according to the invention and / or water-absorbing polymers.

Further preferred release agents are release agents, such as inorganic or organic powder release agents. These release agents are preferably used in amounts ranging from 0 to 2% by weight, more preferably in a range of 0.1 to 1.5% by weight, based on the weight of the hydrogel polymer and / or the water-absorbent polymer used. Preferred release agents are wood flour, pulp fibers, powdered bark, cellulose powder, mineral fillers such as perlite, synthetic fillers such as nylon powder, rayon powder, diatomaceous earth, bentonite, kaolin, zeolites, talc, clay, ash, coal dust, magnesium silicates, fertilizers or mixtures of substances. Highly dispersed pyrogenic silica, as sold under the trade name Aerosil by Evonik Degussa, is preferred. In a further preferred embodiment of the method according to the invention, bringing the hydrogel polymer particles and / or the water-absorbing polymer particles into contact with an effect substance, such as a polysugar, a polyphenolic compound such as hydrolyzable tannins or a silicon-oxygen containing compound or a mixture of at least two effect materials based on it. The effect material can be added both in solid form (powder) and in dissolved form with a solvent, the addition of the effect substance at the earliest after the Process step iii) takes place. As effect material is understood in the context of the present invention, a substance which serves for odor inhibition.

According to the invention, these are understood as meaning poly sugars, among which the person skilled in the art understands those from the group of the known starches and their derivatives, celluloses and their derivatives, cyclodextrins. Cyclodextrins are preferably understood as meaning cyclodextrin, β-cyclodextrin, γ-cyclodextrin or mixtures of these cyclodextrins.

As the silicon-oxygen-containing compounds, zeolites are preferable. As zeolites, it is possible to use all synthetic or natural zeolites known to the person skilled in the art. Preferred natural zeolites are zeolites of the natolite group Harmoton group, the mordenite group, the chabazite group, the faujasite group (sodalite group) or the analcite group. Examples of natural zeolites are Analcim, Leucite, Pollucite, Wairakite, Bellbergite, Bikitaite, Boggsite, Brewsterite, Chabazite, Willhersonite, Cowlesite, Dachiardite, Edingtonite, Epistilbit, Erionite, Faujasite, Ferrierite, Amicite, Garronite, Gismondine, Gobbinsite, Gmelinite, Gonnardite , Goosecreekite, Harmotom, Phillipsite, Wellsite, Clinoptilolite, Heulandite, Laumontite, Levyne, Mazzite, Merlinoite, Montesommaite, Mordenite, Mesolite, Natrolite, Scolecite, Offretite, Paranatrolite, Paulingite, Perlialite, Barrerite, Stilbite, Stellerite, Thomsonite, Chernichite or Yugawaralite , Preferred synthetic zeolites are zeolite A, zeolite X, zeolite Y, zeolite P or the product ABSCENTS®.

As cations, the zeolites used in the process according to the invention preferably contain alkali metal cations such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ or Fr ⁺ and / or alkaline earth metal cations such as Mg ²⁺ , Ca ²⁺ , Sr ² * or Ba ²⁺ .

As zeolites, zeolites of the so-called "middle" type can be used, in which the Si0 ₂ / Al0 ₂ ratio is less than 10, particularly preferably the Si0 ₂ / Al0 ₂ - ratio of these zeolites in a range of 2 to 10. In addition zeolites of the "high" type, which include, for example, the well-known "molecular sieve" zeolites of the type ZSM and zeolite beta, can also be used for these "middle" zeolites. These "high" zeolites are preferably characterized by a Si0 ₂ / Al0 ₂ Ratio of at least 35, more preferably characterized by a Si0 ₂ / Al0 ₂ ratio in a range of 200 to 500. Preferably, the zeolites are used as particles having an average particle size in a range from 1 to 500 μm, more preferably in a range from 2 to 200 μm, and moreover preferably in a range from 5 to 100 μm. The effect substances are preferably used in the process according to the invention in an amount in a range from 0.1 to 50% by weight, more preferably in a range from 1 to 40% by weight and moreover preferably in an amount in the region of 5 to 30% by weight, based in each case on the weight of the hydrogel polymer particles and / or water-absorbing polymer particles.

As germ-inhibiting agents are in principle all active against Gram-positive bacteria substances such. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N '- (3,4-dichlorophenyl) urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4- Chloro-3,5-dimethylphenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- ( 4-chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, Phenoxyethanol, glycerol monocaprinate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as. Salicylic acid n-octylamide or salicylic acid n-decylamide.

For example, esterase inhibitors are suitable as enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen ™ CAT, Cognis GmbH, Dusseldorf / Germany). The substances inhibit the enzyme activity and thereby reduce odors. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.

Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce their propagation speed. It is important that perfume must remain unimpaired. Odor absorbers have no activity against bacteria. They contain, for example, as a main component of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such. B. Extracts of Labdanum or Styrax or certain Abietic acid derivatives. Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g. Benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. The alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg. B. sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil. Preferably bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, alpha -Hexylzimtaldehyd, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, lavandin oil, Muscat Sage oil, beta-damascone, geranium oil bourbon, cyclohexyl salicylate, vertofix coeur, iso-e-super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and floramate alone or in mixtures.

Antiperspirants reduce sweating by affecting the activity of the eccrine sweat glands, thus counteracting underarm wetness and body odor. Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are, for. For example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, Aluminiumiumsesqui- chlorohydrate and their complex compounds z. With propylene glycol-1, 2. Aluminum hydroxyalloinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, Aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds z. With amino acids such as glycine.

As further additives in the context of the present invention, anti-caking compounds such as e.g. Kaolin aerosils and similar insoluble inorganic silicon-based additives such as e.g. Silicas or silica sols, surfactants, e.g. Surfactants, viscosity modifiers or the like mentioned which are applied to the surface of the polymer particles or also react with the free polymer chains of the polymer particle.

For mixing or spraying, all devices are suitable which allow a homogeneous distribution of a solution, powder, suspension or dispersion on or with the hydrogel polymer particles (VP) or water-absorbing polymers. Examples are Lödige mixers (manufactured by Gebrüder Lödige Maschinenbau GmbH), Gericke multi-flux mixers (manufactured by Gericke GmbH), DRAIS mixers (manufactured by DRAIS GmbH Spezialmaschinenfabrik Mannheim), Hosokawa mixers (Hosokawa Mokron Co. Ltd.), Ruberg mixers (manufactured by Gebr. Ruberg GmbH & Co. KG Nieheim), Hüttlin coaters (manufactured by BWI Hüttlin GmbH Steinen), fluidized bed dryers or spray granulators of AMMAG (manufactured by the company AMMAG Gunskirchen, Austria ) or Heinen (manufactured by A. Heinen AG Anlagenbau Varel), Patterson-Kelly mixers, NARA paddle mixers, screw mixers, plate mixers, fluidized bed dryers or Schugi mixers. For bringing into contact in a fluidized bed all known to those skilled and suitable appear fluidized bed method can be applied. For example, a fluidized bed coater can be used.

A further contribution to the solution of the aforementioned object is afforded by the process for the preparation of a water-absorbing polymer, comprising the process steps (i) mixing

(a1) 0.1 to 99.999 wt .-%, preferably 20 to 98.99 wt .-% and particularly preferably

From 30 to 98.95% by weight of polymerisable, ethylenically unsaturated,

acid group-containing monomers or their salts or polymerizable, ethylenically unsaturated, a protonated or quaternized nitrogen

containing monomers, or mixtures thereof, wherein at least ethylenically unsaturated, acid group-containing monomers, preferably acrylic acid-containing

Mixtures are particularly preferred (α2) 0 to 70 wt .-%, preferably 1 to 60 wt .-% and particularly preferably 1 to 40 wt .-% of polymerizable, ethylenically unsaturated, with (a1) copolymerizable monomers,

(a3) 0.001 to 10 wt .-%, preferably 0.01 to 7 wt .-% and particularly preferably 0.05 to 5 wt .-% of one or more crosslinkers,

(a4) 0 to 30 wt .-%, preferably 1 to 20 wt .-% and particularly preferably 5 to 10 wt .-% of water-soluble polymers,

(a5) 0-20 wt .-%, preferably 2.5-15 wt .-% and particularly preferably 5-10 wt .-% water and

(a6) 0 to 20 wt .-%, preferably 0.01 to 7 wt .-% and particularly preferably 0.05 to 5 wt .-% of one or more auxiliaries, wherein the sum of the amounts by weight (a1) to (a5) 100% by weight,

(ii) radical polymerization with crosslinking to give a water-insoluble,

to form aqueous untreated hydrogel polymer,

(iii) drying the hydrogel polymer,

(iv) grinding and screening the hydrogel polymer,

(v) surface postcrosslinking of the ground and sieved hydrogel polymer and

(vi) drying and packaging of the water-absorbing polymer, wherein

0.01 to 10 wt .-%, preferably 0.02 to 8 wt .-% and particularly preferably 0.07 to 7 wt .-% of a salt of an α, β-diunsaturated carboxylic acid, based on the acrylic acid, from the Group of α, β-diunsaturated carboxylic acids with C5 bis

C-14 base bodies are added in at least one of steps (i) to (vi), preferably at least one of steps (iii) to (vi). More preferably, the salt is added to an α, β-diunsaturated carboxylic acid in steps (v) to (vi), preferably in steps (iii) to (vi) and preferably in steps (i) to (vi).

It may be advantageous if in addition to the salt of an α, β-double unsaturated carboxylic acid and free α, β-double unsaturated carboxylic acid is used. Preferably, the free α, β-diunsaturated carboxylic acid is identical to the α, β-diunsaturated carboxylic acid, the salt of which is used. In a preferred embodiment of the present invention, the α, β-diunsaturated carboxylic acid having a C5 to C-14 base and / or its salt in the

Monomer solution after step ii) was added.

In a further preferred embodiment, the α, β-diunsaturated carboxylic acid having a C5 to C-14 basic body and / or its salt in the

Polymer network used after step iii).

In a further particularly preferred embodiment, the addition of the α, β-diunsaturated carboxylic acid with a C5 to C-14 base body and / or its salt is added after step iv) or v).

In a further particularly preferred embodiment, the addition of the α, β-diunsaturated carboxylic acid and / or its salt takes place in the formulation of step (vi).

A further contribution to the solution of the objects described at the outset is provided by a composite comprising the water-absorbing polymers according to the invention or the hydrogel polymers or the water-absorbing polymers or hydrogel polymers obtainable by the processes according to the invention and a substrate. It is preferred that the water-absorbing polymers or hydrogel polymers according to the invention and the substrate are firmly bonded together. As substrates, films of polymers, such as polyethylene, polypropylene or polyamide, metals, nonwovens, fluff, tissues, fabrics, natural or synthetic fibers, or foams are preferred. Furthermore, it is preferred according to the invention that the composite comprises at least one region of water-absorbing polymers or hydrogel polymers in an amount in the range of about 15 to 100 wt .-%, preferably about 30 to 100 wt .-%, particularly preferably of about 50 to 99.99 wt .-%, further preferably from about 60 to 99.99 wt .-% and more preferably from about 70 to 99 wt .-%, each based on the total weight of the relevant area of the composite includes, which range preferably has a size of at least 0.01 cm ³ , preferably at least 0.1 cm ³ and most preferably at least 0.5 cm ³ . A further contribution to the solution of at least one of the abovementioned objects is provided by a process for producing a composite, wherein the water-absorbing polymers according to the invention or the superabsorbent obtainable by the process according to the invention and a substrate and optionally an additive are brought into contact with one another. The substrates used are preferably those substrates which have already been mentioned above in connection with the composite according to the invention.

A contribution to the solution of at least one of the abovementioned objects is also provided by a composite obtainable by the process described above, this composite preferably having the same properties as the composite according to the invention described above.

A further contribution to the solution of at least one of the abovementioned objects is provided by chemical products comprising the water-absorbing polymers or hydrogel polymers according to the invention or a composite according to the invention. Preferred chemical products are, in particular, foams, shaped articles, fibers, films, cables, sealing materials, liquid-absorbent hygiene articles, in particular diapers and sanitary napkins, carriers for plant- or fungi-growth-regulating agents or crop protection active ingredients, additives for building materials, packaging materials or floor additives.

The use of the water-absorbing polymers or of the composite according to the invention in chemical products, preferably in the abovementioned chemical products, in particular in hygiene articles such as diapers or sanitary napkins, and the use of the water-absorbing polymer particles as a carrier for plant or fungi growth-regulating agents or crop protection active ingredients contribute to solve at least one of the objects mentioned above. When used as a carrier for plant or fungi growth regulating agents or crop protection actives, it is preferred that the plant or fungi growth regulating agents or crop protection actives can be delivered for a period of time controlled by the carrier.

TEST METHODS

Unless otherwise stated below, the measurements herein are made according to the ERT method. "ERT" stands for EDANA Recommended Test and "EDANA" for European Disposable and Nonwoven Association. All test methods are basically, though Unless otherwise stated, be carried out at an ambient temperature of 23 + 2 ° C and a relative humidity of 50 + 10%.

Particle Size Distribution (PSD Particle Size Distribution)

The particle size distribution of the water-absorbing polymer particles is determined analogously to the EDANA-recommended test method no. WSP 220.3-10 "Particle Size Distribution".

Centrifuge Retention Capacity (CRC) The centrifuge retention capacity was determined according to the EDANA (European Disposables and Nonwovens Association) recommended test method no. WSP 241 .3-10 "Centrifuge retention capacity".

Absorption against a pressure of 0.7 psi (AAP)

The absorption under pressure was determined as AAP (Absorption Against Pressure) according to WSP 242.3-10 on the total grain fraction. Accordingly, 0.90 g of the test substance (sieved between 150 and δδθμηη) was weighed into a test cylinder of 60.0 mm in inner diameter and a sieve bottom (400 mesh) (concentration: 0.032 g / cm ² ) and evenly distributed. A cylindrical weight of 50 g / cm ² = 0.7 psi) with an outside diameter of 59.2 mm is placed on the test substance. In a plastic bowl filter plates are placed, which are covered with a filter paper. The plastic dish is filled with 0.9% NaCl solution until the liquid level is flush with the top edge of the filter plates. Subsequently, the prepared measuring units are placed on the filter plates. After a swelling time of 60 minutes, the measuring units are removed and the weight removed. The amount of liquid absorbed is determined gravimetrically and converted to 1 gram of test substance.

Determination of NH3 release (Proteus mirabilis):

Proteus mirabilis was grown overnight at 37 ° C on a Caso slant agar. The bacterial culture was treated with 5 ml of synthetic urine (25 g / l urea, 9 g / l sodium chloride, 5 g / l glucose, 4 g / l potassium sulfate, 2.5 g / l ammonium sulfate, 0.7 g / l calcium acetate, 0 , 7 g / l magnesium sulfate x 7 H ₂ 0, 0.5 g / l yeast extract, 5 g / l meat extract, 5 g / l peptone). The germ count of the synthetic urine was adjusted so that an initial bacterial count of about 10 ⁵ CFU / ml urine was present. In each case 33 ml of the bacteria-added artificial urine were transferred to Erlenmeyer flasks and admixed with 1 g of superabsorber. The vessels were covered with a rubber stopper through which Bore a Dräger - diffusion tube (ammonia 20 / aD) was performed, sealed and incubated at 37 ° C in an incubator. The released ammonia was measured in ppm xh. Examples

The following examples serve to illustrate the invention without, however, limiting it thereto. For the following inventive examples, a defined particle size distribution (PSD) was used (150μηι to 850μη "ΐ).

The term "SX" as used in the description refers to the thermal surface postcrosslinking of the precursor (VP) .The precursor corresponds to the hydrogel polymer produced after the first drying, with the aforementioned particle size distribution.

Description of the production of SAP samples

Polymer (powder A)

A monomer solution consisting of 300 g of acrylic acid (which was neutralized to 70 mol% with 233.14 g of 50% NaOH), 442.81 g of water, 0.645 g of polyethylene glycol 300 diacrylate, 1 .1 g of monoallylpolyethyleneglycol-450-monoacrylic acid ester was degassed using nitrogen and freed of dissolved oxygen and cooled to the starting temperature of about 4 ° C. After the starting temperature was reached, the addition of an initiator solution (0.3 g of sodium peroxodisulfate in 10 g of water, 0.07 g of 35% hydrogen peroxide solution in 10 g of water and 0.015 g of ascorbic acid in 2 g of water). The subsequent exothermic polymerization reaction had an adiabatic final temperature of about 100 ° C. The resulting hydrogel was comminuted with a laboratory meat grinder (5 mm perforated disc) and the crushed sample dried for two hours at 150 ° C in a laboratory circulating air dryer. The dried polymer was first roughly crushed and then ground using a SM100 granulator with a 2 mm grain perforation and sieved to a powder having a particle size of 150 to 850 μm.

Example 1 (reference sample):

100 g of powder A were coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water, the solution being applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. The coated powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Examples 2 - 10: Addition of sorbic acid salts / sorbic acid in the surface postcrosslinking step (as a powder or as an aqueous solution):

Example 2:

100 g of the powder A were coated with a solution of 1, 0 g of ethylene carbonate and 3.0 g of deionized water and 1, 0 g potassium sorbate wherein the solution with a syringe (0.45 mm cannula) was applied to the located in the mixer polymer powder. The coated powder was then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 3:

According to Example 2, the procedure was only with the difference that was coated with 1, 5 g of potassium sorbate. Example 4:

100 g of the powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water and 2.0 g of potassium sorbate. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. The coated powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 5:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. Subsequently, 1, 0 g of potassium sorbate were added as a fine powder and homogenized for 3 hours on the overhead shaker. The homogenized powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 6:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. Then, 1.5 g of potassium sorbate were added as a fine powder and homogenized on the overhead shaker for 3 hours. The homogenized powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 7:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. Subsequently, 2.0 g of potassium sorbate were added as a fine powder and homogenized on the overhead shaker for 3 hours. The homogenized powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 8:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. Then, 1.5 g of calcium sorbate were added as a fine powder and 3 hours on the overhead shaker homogenized. The homogenized powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 9:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. Then, 1.0 g of sorbic acid was added as a fine powder and homogenized on the overhead shaker for 3 hours. The homogenized powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Example 10:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. Subsequently, 1, 5 g of sorbic acid were added as a fine powder and homogenized for 3 hours on the overhead shaker. The homogenized powder is then heated in a drying oven at 170 ° C for a period of 90 minutes.

Examples 1 1 - 14: Addition of sorbic acid salts in the preparation step (as powder or as aqueous solution): Example 1 1:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. The coated powder is then heated in a drying oven at 170 ° C over a period of 90 minutes and surface-crosslinked. Subsequently, 1, 0 g of potassium sorbate are added as a fine powder and homogenized for 3 hours on the overhead shaker.

Example 12:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. The coated powder is then heated in a drying oven at 170 ° C. over a period of 90 minutes and surface crosslinked. Subsequently, 2.0 g of potassium sorbate are added as a fine powder and homogenized on the overhead shaker for 3 hours.

Example 13:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. The coated powder is then heated in a drying oven at 170 ° C. over a period of 90 minutes and surface-crosslinked. Subsequently, 2.5 g of a 40 percent aqueous potassium sorbate solution are added (with a syringe, 0.45 mm cannula) and homogenized on the overhead shaker for 3 hours.

Example 14:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is applied with a syringe (0.45 mm cannula) to the polymer powder in the mixer. The coated powder is then heated in a drying oven at 170 ° C. over a period of 90 minutes and surface-crosslinked. Subsequently, 5.0 g of a 40 percent aqueous potassium sorbate solution are added (with a syringe, 0.45 mm cannula) and homogenized on the overhead shaker for 3 hours. Example 15:

100 g of powder A are coated with a solution of 1.0 g of ethylene carbonate and 3.0 g of deionized water. The solution is taken with a syringe (0.45 mm cannula) applied to the polymer powder in the mixer The coated powder is then heated in a drying oven at 170 ° C over a period of 90 minutes and surface-crosslinked. Subsequently, 7.5 g of a 20 percent aqueous potassium sorbate solution are added (with a syringe, 0.45 mm cannula) and homogenized for 3 hours by means of an overhead shaker.

Sample name Retention [g / g] AAP 0.7 psi [g / g] NH3 delay

Release [h]

Example 1 1 29.3 20.8 10

Example 12 28.6 20.0 12

Example 13 28.7 20.2 1 1

Example 14 28.8 18.6 19

Example 15 28.0 22.2 12

Claims

claims

Water-absorbing polymer based on:

(a2) 0-80% by weight, preferably 0-44.99% by weight and particularly preferably 0.1-44.89% by weight of polymerized, monoethylenically unsaturated monomers copolymerizable with (α1),

(a3) 0.001-5% by weight, preferably 0.01-3% by weight and particularly preferably 0.01-2.5% by weight of one or more crosslinkers,

(a4) 0-30% by weight, preferably 0-5% by weight and particularly preferably 0.1-5% by weight of a water-soluble polymer,

(a5) 0-20 wt .-%, preferably 2.5-15 wt .-% and particularly preferably 5- 10 wt .-% water, and

(a6) 0-20 wt .-%, preferably 0-10 wt .-% and particularly preferably 0.1 to 8 wt .-% of one or more auxiliaries, wherein the sum of the amounts by weight of (a1) to (a6) 100 wt .-% is,

in which

the water-absorbing polymer with 0.001 to 10 wt .-%, preferably 0.02 to 8 wt .-% and particularly preferably 0.07 to 7 wt .-% of a salt of an α, β-unsaturated carboxylic acid, based on the acrylic acid according to the Polymerization is treated.

Water-absorbing polymers according to claim 1, characterized in that the water-absorbing polymer is most preferably treated with 0.001 to 1, 5 wt .-%, of a salt of an α, β-unsaturated carboxylic acid, based on the acrylic acid after the polymerization.

Water-absorbing polymers according to any one of claims 1 or 2, characterized in that the water-absorbing polymer has preferably been treated with the salt of an α, β-unsaturated carboxylic acid from the group of α, β-diunsaturated carboxylic acids having C5 to C-14 basic body is. Water-absorbing polymers according to one of the preceding claims, characterized in that in addition to a salt of an α, β-diunsaturated carboxylic acids having a C5 to C-14 basic body, optionally an acid from the

Group of α, β-diunsaturated carboxylic acids with C5 to C-14 base body is present.

Water-absorbing polymers according to one of the preceding claims, characterized in that as α, β-diunsaturated carboxylic acids with C5 to C-14

Basic bodies are those selected from the group of hexadienoic, heptadiene, octadiene, nonadiene, decadiene, unodecadiene, dodecadiene, tridecadiene, - or tetradecadienoic acid or their isomers or stereoisomers.

Water-absorbing polymers according to any one of the preceding claims, characterized in that the free acid is equal to that of the salt of α, β-diunsaturated carboxylic acids having a C5 to C-14 base body.

Water-absorbing polymers according to any one of the preceding claims, characterized in that the aqueous monomer solution contains at least one salt from the group of α, β-diunsaturated carboxylic acids having C5 to C-14 base body, based on the water-absorbing polymer, wherein the salts of the group of monovalent, divalent and trivalent metal cations.

Water-absorbing polymers according to one of the preceding claims, characterized in that the metals used are sodium, potassium, cesium, rubidium, magnesium, calcium, strontium, barium, aluminum, gallium, indium.

Water-absorbing polymers according to any one of the preceding claims, characterized in that preferably a salt from the group of α, β-diunsaturated carboxylic acids having a C5 to C-14 base body and with a

Counterion from the group of sodium, potassium, magnesium, calcium, strontium, barium, or aluminum is used.

10. Water-absorbing polymers according to any one of the preceding claims, characterized in that as α, β-double unsaturated carboxylic acid with a C5 bis

C-14 base body preferably sorbic acid is used.

1 1. Water-absorbing polymers according to any one of the preceding claims, characterized in that preferably an alkali metal salt of an α, β-double unsaturated carboxylic acid having a C5 to C-14 base body is used.

12. Water-absorbing polymers according to any one of the preceding claims, characterized in that preferably an alkaline earth metal salt of an α, β-diunsaturated carboxylic acid having a Cg to C-14 basic body is used.

13. A process for producing water-absorbent polymers, comprising the process steps

(i) mixing

(a1) 0.1 to 99.999% by weight, preferably 20 to 98.99% by weight and particularly preferably 30 to 98.95% by weight of polymerisable, ethylenically unsaturated,

containing monomers, or mixtures thereof, wherein at least ethylenically unsaturated, acid group-containing monomers, preferably acrylic acid-containing mixtures are particularly preferred,

(a2) 0 to 70 wt .-%, preferably 1 to 60 wt .-% and particularly preferably 1 to 40 wt .-% of polymerizable, ethylenically unsaturated, with (a1) copolymerizable monomers,

(a5) 0-20 wt .-%, preferably 2.5-15 wt .-% and particularly preferably 5-10 wt% water, and

(a6) 0-20 wt .-%, preferably 0-10 wt .-% and particularly preferably 0.1 to 8% by weight of one or more auxiliaries, wherein the sum of the amounts by weight of (a1) to (a6) 100 wt .-% is (ii) free radical polymerization with crosslinking to form a water insoluble, aqueous untreated hydrogel polymer,

(iii) drying the hydrogel polymer,

(iv) grinding and screening the hydrogel polymer,

(v) surface postcrosslinking of the ground and sieved hydrogel polymer and

(vi) drying and packaging of the water-absorbing polymer, wherein

0.001 to 10 wt .-%, preferably 0.02 to 8 wt .-% and particularly preferably 0.07 to 7 wt .-% of at least one salt of an α, β-diunsaturated carboxylic acid, based on the acrylic acid, from the group of α, β-diunsaturated carboxylic acids having C5 to C-14 basic body in at least one of the steps (i) to (vi) are added.

A method according to claim 13, characterized in that the water-absorbing polymer is most preferably treated with 0.01 to 1, 5 wt .-%, of a salt of an α, β-unsaturated carboxylic acid, based on the acrylic acid after the polymerization.

Method according to one of the preceding claims, characterized in that in addition to a salt optionally an acid from the group of α, β-diunsaturated carboxylic acids having a C5 to C-14 base body is present.

Method according to one of the preceding claims, characterized in that the acid optionally corresponds to that of the salt or another acid from the group of α, β-double unsaturated carboxylic acids having C5 to C-14 base body.

Method according to one of the preceding claims, characterized in that the aqueous monomer solution contains at least one salt from the group of α, β-double unsaturated carboxylic acids having C5 to C-14 base body, based on the water-absorbing polymer, wherein the salts of the group of monovalent, divalent and trivalent metal cations.

18. The method according to any one of the preceding claims, characterized in that as metals sodium, potassium, cesium, rubidium, magnesium, calcium, strontium, barium, aluminum, gallium, indium is used.

Method according to one of the preceding claims, characterized in that preferably a salt from the group of α, β-diunsaturated carboxylic acids having a C5 to C-14 base body and with a counterion from the group of sodium,

Potassium, magnesium, calcium, strontium, barium, or aluminum is used.

Method according to one of the preceding claims, characterized in that is preferably used as α, β-double unsaturated carboxylic acid having a C5 to C-14 base body sorbic acid.

Method according to one of the preceding claims, characterized in that preferably an alkali metal salt of an α, β-diunsaturated carboxylic acid having a C5 bis

C-14 base body is used.

22. A water-absorbing polymer obtainable according to any one of claims 1 to 21. 23. composite comprising a water-absorbing polymer according to one of the preceding claims.

24. A process for producing a composite, wherein a water-absorbing polymer according to any one of the preceding claims and an aid are brought into contact with each other.

25. Composite, obtainable by a process according to claim 24.

26. Foams, shaped bodies, fibers, films, films, cables, sealing materials, liquid-absorbent hygiene articles, carriers for plant and fungi growth-regulating agents, packaging materials, floor additives or building materials, comprising the water-absorbing polymer according to one of claims 1 to 21 or the composite according to claim 23 27. The use of the water-absorbing polymer according to any one of claims 1 to 21 or a composite containing a water-absorbing polymer according to claim 23 in foams, moldings, fibers, films, films, cables, Sealing materials, liquid-absorbent hygiene articles, carriers for plant and fungi growth regulating agents, packaging materials, bottom additives, for the controlled release of active substances or in building materials.