WO2011032876A1 - Color-stable superabsorber - Google Patents

Abstract

The invention relates to a superabsorber comprising at least one stabilizer against discoloration, selected from phenols, phosphonic acid (HP(O)(OH)₂), phosphoric acid (H₃PO₃), and the salts and esters of said acids, having improved stability against discoloration during storage at elevated temperatures or elevated humidity.

Description

 The present invention relates to a color-stable superabsorber, a process for its preparation and its use and hygiene articles containing it. A color-stable superabsorber is to be understood as meaning a superabsorber which does not discolor or only in a comparatively small extent when stored under elevated temperature and atmospheric humidity.

Superabsorbents are known. Also, for such materials, terms such as "high swellable polymer" "hydrogel" (often used for the dry form), "hydrogel-forming polymer", "water-absorbent polymer", "absorbent gelling material", "swellable resin", "water-absorbent resin These are crosslinked hydrophilic polymers, in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose partially cross-linked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives, with water-absorbing polymers based on partially neutralized acrylic acid being the most widespread.The essential properties of superabsorbents are their ability to multiply their own weight of aqueous liquid absorb the fluid and even under some pressure not to give the liquid again. The superabsorber, which is used in the form of a dry powder, transforms into a gel when it absorbs liquid, and accordingly turns into a hydrogel during normal water absorption. Crosslinking is essential for synthetic superabsorbents and an important difference to conventional pure thickeners, as it leads to the insolubility of the polymers in water. Soluble substances would not be useful as superabsorbent. By far the most important application of superabsorbents is the absorption of body fluids. Superabsorbents are used, for example, in infant diapers, adult incontinence products or feminine hygiene products. Other fields of application are, for example, the water-retaining agents in agricultural horticulture, as water storage for protection against fire, for liquid absorption in food packaging or, more generally, for the absorption of moisture.

Superabsorbents can absorb a multiple of their own weight of water and retain it under some pressure. In general, such a superabsorber has a CRC ("Centrifuge Retention Capacity", measuring method, see below) of at least 5 g / g, preferably at least 10 g / g and in a particularly preferred form at least 15 g / g. can also be a mixture of materially different individual superabsorbers or a mixture of components that show superabsorbent properties only in combination, it comes here less on the material composition than on the superabsorbent properties.

Important for a superabsorbent is not only its absorption capacity, but also the ability to retain fluid under pressure (retention, usually expressed as "absorption under load" ("AUL") or "absorption against pressure" ("AAP"), method of measurement, see below ) as well as the liquid transport in the swollen state (usually expressed as "Saline Flow Conductivity" ("SFC"), measurement method see below). Swollen gel can hinder liquid transport to superabsorbers that have not yet swollen ("gel blocking") .Good transport properties for liquids include, for example, hydrogels which have a high gel strength in the swollen state Gels with only low gel strength are under an applied pressure ( Body pressure) deforms, clogs pores in the superabsorbent / cellulose fiber absorbent body and thus prevents further absorption of fluid.A higher gel strength is usually achieved by a higher degree of cross-linking, which, however, reduces the absorption capacity of the product.An elegant method for increasing the gel strength represents the increase in the degree of crosslinking on the surface of the superabsorbent particles in relation to the interior of the particles. For this purpose, in a surface postcrosslinking step, dried superabsorbent particles having an average crosslinking density are usually introduced he subjected additional crosslinking in a thin surface layer of their particles. Surface postcrosslinking increases the crosslink density in the shell of the superabsorbent particles, raising the absorption under pressure to a higher level. While the absorption capacity in the surface layer of the superabsorbent particles decreases, their core has an improved absorption capacity compared to the shell due to the presence of mobile polymer chains, so that the shell construction ensures improved fluid transfer without gel blocking occurring. It is also known to produce super-crosslinked superabsorbers overall and to subsequently reduce the degree of crosslinking in the interior of the particles compared to an outer shell of the particles.

Also, processes for the production of superabsorbents are known. Acrylic acid-based superabsorbents, which are most commonly used in the marketplace, are prepared by free-radical polymerization of acrylic acid in the presence of a crosslinker (the "internal crosslinker"), the acrylic acid before, after or partly before, partly after the polymerization The polymer gel obtained in this way is comminuted (depending on the polymerization reactor used, this can be done simultaneously with the polymerization) and dried.The dry powder obtained in this way (the "base polymer" or "polymer") is neutralized to a certain degree. Basispolymer ") is usually postcrosslinked on the surface of the particles by reacting with other crosslinkers such as organic crosslinkers or polyvalent cations, for example aluminum (usually as aluminum sulfate used) or both is implemented in order to produce a more crosslinked surface layer relative to the particle interior.

A common problem with superabsorbents is discoloration, which occurs when storing under higher temperature or higher humidity. Such conditions often occur during storage of superabsorbers in tropical or subtropical countries. Under such conditions, superabsorbents tend to yellow, they may even take on brown or almost black coloring. This discoloration of the actually colorless superabsorbent powder is unsightly and undesirable because it is particularly visible in the desired thin hygiene products and

 Consumers reject unsightly hygiene products. The cause of the discoloration is not fully understood, however, reactive compounds such as residual monomers from the polymerization, the use of some initiators, impurities of the monomer or the neutralizing agent, surface postcrosslinkers or stabilizers of the monomers used seem to play a role.

Fredric L. Buchholz and Andrew T. Graham (ed.), In: "Modern Superabsorbent Polymer Technology", J. Wiley & Sons, New York, USA / Wiley-VCH, Weinheim, Germany, 1997, ISBN 0-471 -1941 In Section 2.7.2, it is also mentioned that calcium ions are known as ionic crosslinkers of superabsorbers, but only trivalent ions such as aluminum would be useful crosslinkers WO 2005/073 260 A1 discloses that in the preparation of superabsorbers by polymerization of supersaturated solutions, sodium acrylate monomer can be wholly or partly replaced by salts, such as magnesium, calcium, strontium or barium acrylate WO 2005/01 1860 shares the known Internal crosslinkers for superabsorbents in various crosslinker classes, one in which polyvalent metal cations are summarized, including, inter alia, as a divalent cation magnesium, calcium and strontium, but the trivalent aluminum is generally preferred.

WO 2008/055856 A1 teaches the avoidance of discolorations of a superabsorber which are caused by excessively high iron content of the sodium hydroxide solution used to partially neutralize the acrylic acid in the preparation of the superabsorber by adding phosphoric acid or phosphate salts. JP 05/086 251 A teaches the use of phosphoric acid derivatives or salts thereof, in particular 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or their alkali metal or ammonium salts as stabilizers of superabsorbers against discoloration. WO 03/059 962 A1 or the equivalent patent application US 2005/0085604 A1 discloses the use of The use of metal chelating agents in any step of the superabsorbent production and the addition of a reducing or oxidizing agent before drying of the aqueous polymer as measures against discoloration.

WO 03/014 172 A2 relates to the production of superabsorbers from highly pure acrylic acid, which has been freed to prevent discoloration of the superabsorbent in particular of aldehydes. WO 00/55245 A1 teaches the stabilization of superabsorbents against discoloration by treatment with an inorganic reducing agent and optionally a metal salt, such as an alkaline earth salt, which is added after the polymerization. The inorganic reducing agent is typically a hypophosphite, phosphite, bisulfite or sulfite. The metal salt is typically a colorless (the property "colorless" is often simply called "white"), phosphate, acetate or lactate, but not a halide. According to the teaching of WO 2006/058 682, discolorations of superabsorbents are avoided when the drying and the post-crosslinking reaction are carried out in an atmosphere which is substantially free of oxidizing gases.

EP 505 163 A1 discloses the use of a combination of surface-active substance and a compound which adds to double bonds, for example unsubstituted or substituted alkyl- or arylsulfinic acids or salts thereof for reducing residual monomers in superabsorbers. EP 668 080 A2 and the divisional application EP 1570 869 A1 relate to the use of organic acids, including sulfinic acids, but exclusively of salts of organic acids or sulfinic acids, or of polyamino acids or their salts to reduce residual surface postcrosslinkers, in particular of surface postcrosslinkers Epoxy compounds, after surface postcrosslinking. EP 386 897 A2,

EP 441 975 A1 and EP 605 215 A1 teach the use of sulfites, hydrogen sulfites or thiosulfates for reducing residual monomers from the polymerization. EP 1 645 596 A1 teaches the stabilization of superabsorbers against discoloration by addition of an inorganic salt, an aminocarboxylic acid chelating agent and an organic antioxidant. As the inorganic salt, sulfites, bisulfites, pyrosulfites, dithionites, trithionates, tetrathionates, thiosulfates or nitrites are used. EP 1 577 349 A1 teaches the use of these salts for the same purpose, but the content of the superabsorbent treated with iron is kept below 1 ppm by weight.

WO 2009/060062 or earlier International Patent Application Serial No. PCT / EP2009 / 059793 teach the addition of sulfinic acid derivatives to superabsorbents to stabilize them against discoloration. WO 2008/092 842 A1 teaches the addition of a basic salt of a divalent metal cation to superabsorbers, inter alia, in order to increase the stability against discoloration. WO 2008/092 843 A1 discloses the use of carboxylic acid salts and / or basic salts of trivalent metal cations for the same purpose. WO 2005/054 356 A1 teaches the use of steric Hindered phenols instead of the technically usual para-methoxyphenol ("methyl hydroquinone", "MEHQ") as stabilizers for acrylic acid against polymerization, which have the advantage of less discoloration of the polymer. Another object is to find other or even better superabsorbers which are stabilized against discoloration, in particular against yellowing or browning when stored under elevated temperature and / or elevated air humidity. The

Useful properties of the superabsorber, in particular its ability to absorb liquid, even under pressure, as well as its ability to convey liquid, should not be impaired or at least not significantly impaired. Likewise, other properties should not be affected, such as odor, which may be a problem with sulfur-containing reducing agents in the presence of moisture, or its flowability, which may be a problem with sodium hypophosphite additive, or dusting, which can be a problem when adding insoluble calcium salts , Further objects of the invention are finding a method for producing such a superabsorbent and uses of this superabsorbent.

The object was achieved by a superabsorber containing at least one stabilizer against discoloration, which consists of phenols, phosphonic acid (HP (0) (OH) 2),

Phosphorus acid (H3PO3), and the salts and esters of these acids is selected. Furthermore, a process for the preparation of this superabsorbent, uses of this superabsorbent as well as hygiene articles containing this superabsorber and processes for their preparation have been found.

The superabsorbers according to the invention show surprisingly good stability against discoloration without their use properties such as CRC, AUL or SFC being significantly impaired. According to the invention, at least one stabilizer against discoloration is added to the SAP.

The stabilizer can be added in any form. Mostly it is preferred to add it in predominantly undissolved form. "Predominantly undissolved" means that in general at least 50% by weight, preferably at least 70% by weight and in a particularly preferred form at least 90% by weight of the amount of stabilizer added does not occur at the time of addition The stabilizer is added either as a dry powder or as a suspension in a suspending agent The stabilizer can be added to the superabsorbent at any time during preparation Preferably, it is not added to the monomer mixture for polymerization or to a monomer but instead only when crosslinked polymer is present is, at the earliest during the polymerization. It can be added, for example, during the polymerization, during a surface postcrosslinking or after the surface postcrosslinking. In any case, if the stabilizer is added to the monomer mixture or to a monomer, it is additionally added to any stabilizer against undesired or premature polymerization. In particular, when the stabilizer is a sterically hindered phenol, it is preferred to add it at the earliest during the polymerization.

The stabilizer is soluble or insoluble. Preferably, the stabilizer is insoluble in water, i. its solubility in water at 25 ° C is at most 5 g / l, preferably at most 1 g / l.

The stabilizer (or stabilizers) is made from phenols, phosphonic acid

(HP (0) (OH) 2), phosphorous acid (H3PO3) and the salts and esters of these acids.

Among the phenols, the sterically hindered phenols are preferred. Hindered phenols are understood as meaning phenols which have a single or double-branched substituent, preferably a double-branched substituent, at least in the 2-position and optionally also in the 6-position on the phenyl ring. Branched substituents are understood to mean substituents which bear at least two radicals other than hydrogen on the atom bonded to the phenyl ring of the phenol, apart from the C atom of the phenyl ring to which they are attached. However, sterically hindered phenols are also those which carry a sterically demanding unbranched substituent at least in the 2-position and optionally also in the 6-position. These are understood to mean substituents which comprise at least 6, preferably at least 8, and in a particularly preferred form at least 12 atoms other than hydrogen, but only one on the atom bound to the phenyl ring of the phenol other than the C atom of the phenyl ring to which they are attached of hydrogen other residue. The simplest examples of singly branched substituents are secondary alkyl radicals such as 2-propyl, 2-butyl, 2-pentyl, 3-pentyl, ethylhexyl or cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl or aromatic radicals such as phenyl. The simplest examples of di-branched substituents are tertiary alkyl radicals such as tert-butyl, tert-pentyl or norbornyl. The simplest examples of unbranched radicals are hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, but also neo-pentyl, neo-hexyl or dodecylthiomethyl. All of these radicals can also be substituted or contain atoms other than carbon and hydrogen. The phenyl ring of the phenol may optionally carry further substituents in addition to the substituent in the 2-position and optionally in the 6-position. Examples of preferred sterically hindered phenols are 2-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methyl-phenol (also referred to as 2,6-di-tert tert-butyl-para-cresol or 3,5-di-tert-butyl-4-hydroxytoluene), 3,5-di-tert-butyl-4- hydroxyphenylacetic acid, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid and the esters of these acids with alcohols and polyols, for example their simple or multiple esters with glycol, glycerol, 1, 2- or 1, 3-propanediol, trimethylolpropane or Pentaerythritol, such as pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) or octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 4,4-thio-bis (6-tert-butyl meta-cresol), 4,6-bis (dodecylthiomethyl) ortho-cresol, 3,3 ', 3 ", 5,5', 5 '"-Hexa-tert-butyl-α; a ', a "- (mesitylene-2,4,6-triyl) tri-para-cresol (other name for 2,4,6-tri [(4-hydroxy-3,5-di-tert-butylphenyl) methyl] mesitylene, CAS no. 1709-70-2, from Ciba Specialty Chemicals, Basel, Switzerland AG, under the brand name Irganox ^® available), N, N-hexane-1 1330 3- diylbis (3- (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,2'-ethylidenebis [4,6-bis (1,1-dimethylethyl) phenol] and ethylenebis (oxyethylene) bis-3- (5-tert .-butyl-4-hydroxy-m-tolyl) -.. propionate) (CAS No. 36443-68-2, from Ciba Specialty Chemicals, Basel, Switzerland AG, sold under the trademark Irganox ^® 245) Further inventively suitable stabilizers are Salts and esters of

 Phosphonic acid (HP (0) (OH) 2) and phosphorous acid (H3PO3) as well as phosphonic acid itself. Phosphonic acid is tautomeric with phosphorous acid, the latter does not exist as free acid. Genuine derivatives of phosphorous acid are only their triesters, commonly referred to as phosphites. The tautomeric phosphonic acid derivatives are commonly referred to as phosphonates. For example, all primary and secondary phosphonates of the alkali metals, including ammonium, and the alkaline earth metals are suitable. Also suitable, for example, are aqueous solutions of phosphonic acid which contain primary and / or secondary phosphonations and at least one cation selected from sodium, potassium, calcium, strontium. Examples of suitable phosphites or phosphonates are calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate], tris (2,4-di-tert-butylphenyl) phosphite, 3.9- Bis (octa-decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and bis (2,4-di-tert-butylphenol) pentaerythritol diphosphite. Stabilizers may simultaneously be phosphonates or phosphites and hindered phenols.

The stabilizers are, unless they are dissolved, naturally particulate, they are therefore predominantly in powder form when applied. The average particle size is typically in the range of at least 0.001 μηη, preferably at least 0.002 μηη, more preferably at least 0.005, and most preferably at least 0.01 μηη, and generally at most 500 μ, preferably at most 200 μηη, more preferably Form at most 100 μηη and in a very particularly preferred form of at most 50 μηη. The particles themselves may be aggregates or agglomerates of smaller primary particles. The particle size can be determined by means of sieve analysis, but it is simpler and therefore preferred to determine the particle size by means of laser diffraction technology. These methods are well known and routinely performed on suitable and commercially available equipment. The anti-discoloration stabilizers mentioned above, when added, are generally present in amounts of at least 0.0001% by weight, preferably at least 0.001% by weight, and most preferably at least 0.025% by weight, and in the formula Generally at most 3% by weight, in a preferred form at most 2% by weight and in a particularly preferred form at most 0.5% by weight, in each case based on the total weight of the superabsorbent according to the invention. According to the invention, each superabsorber can be mixed with the stabilizer. In general, such superabsorbents are crosslinked hydrophilic polymers, in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or in aqueous Liquid swellable natural products such as guar derivatives. Preferably, a superabsorbent based on partially neutralized acrylic acid is used. Superabsorbents are characterized above all by their ability to absorb and retain liquids. An inventive and preferred superabsorbent is prepared, for example, by aqueous solution polymerization of a monomer mixture comprising: a) at least one ethylenically unsaturated monomer bearing at least one acid group, which is optionally present at least partially as a salt,

b) at least one crosslinker,

c) at least one initiator,

d) optionally one or more ethylenically unsaturated monomers copolymerizable with the monomers mentioned under a) and

e) optionally one or more water-soluble polymers.

The monomers a) are preferably water-soluble, i. the solubility in water at 23 ° C. is typically at least 1 g / 100 g of water, preferably at least 5 g / 100 g of water, more preferably at least 25 g / 100 g of water, most preferably at least 35 g / 100 g of water.

Suitable monomers a) are, for example, ethylenically unsaturated carboxylic acids or their salts, such as acrylic acid, methacrylic acid, maleic acid or its salts, maleic anhydride and itaconic acid or their salts. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.

Further suitable monomers a) are, for example, ethylenically unsaturated sulfonic acids, such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Impurities can have a significant influence on the polymerization. Therefore, the raw materials used should have the highest possible purity. It is therefore often advantageous to purify the monomers a) specifically. Suitable purification processes are described, for example, in WO 2002/055469 A1, WO 2003/078378 A1 and WO 2004/035514 A1. A suitable monomer a) is, for example, an acrylic acid purified according to WO 2004/035514 A1 with 99.8460% by weight of acrylic acid, 0.0950% by weight of acetic acid, 0.0332% by weight of water, 0.0203% by weight. % Propionic acid, 0.0001% by weight of furfurals, 0.0001% by weight of maleic anhydride, 0.0003% by weight of diacrylic acid and 0.0050% by weight of hydroquinone monomethyl ether.

The proportion of acrylic acid and / or salts thereof in the total amount of monomers a) is preferably at least 50 mol%, particularly preferably at least 90 mol%, very particularly preferably at least 95 mol%.

The monomer solution preferably contains at most 250 ppm by weight, preferably at most 130 ppm by weight, more preferably at most 70 ppm by weight and preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, in particular by 50% by weight. ppm, hydroquinone half ethers, based in each case on the unneutralized monomer a), where neutralized monomer a), ie a salt of the monomer a) is mathematically taken into account as unneutralized monomer. For example, an ethylenically unsaturated, acid group-carrying monomer having a corresponding content of hydroquinone half-ether can be used to prepare the monomer solution.

Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or alpha-tocopherol (vitamin E).

Suitable crosslinkers b) are compounds having at least two groups suitable for crosslinking. Such groups are, for example, ethylenically unsaturated groups which can be radically copolymerized into the polymer chain, and functional groups which can form covalent bonds with the acid groups of the monomer a). Furthermore, polyvalent metal salts which can form coordinative bonds with at least two acid groups of the monomer a) are also suitable as crosslinking agents b).

Crosslinkers b) are preferably compounds having at least two polymerizable groups which can be incorporated in the polymer network in free-radically polymerized form. Suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallylammonium chloride, tetraallyloxyethane, as described in EP 530 438 A1, di- and triacrylates, as in EP 547 847 A1, EP 559 476 A1 , EP 632 068 A1, WO 93/21237 A1, WO 2003/104299 A1, WO 2003/104300 A1, WO 2003/104301 A1 and DE 103 31 450 A1, mixed acrylates which, in addition to acrylate groups, contain further ethylenically unsaturated groups, as in DE 103 31 456 A1 and US Pat DE 103 55 401 A1, or crosslinker mixtures, as described, for example, in DE 195 43 368 A1, DE 196 46 484 A1, WO 90/15830 A1 and WO 2002/32962 A2.

Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraallyloxyethane, methylene bismethacrylamide, trimethylolpropane triacrylate 15 to 20 times ethoxylated, 15-20 times ethoxylated glycerol triacrylate, polyethylene glycol diacrylate having between 4 and 45 - Ch Ch O units in the molecular chain, trimethylolpropane triacrylate and triallylamine.

Very particularly preferred crosslinkers b) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in WO 2003/104301 A1. Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol. Very particular preference is given to diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol. Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerol, in particular the triacrylate of 3-times ethoxylated glycerol.

The amount of crosslinker b) is preferably from 0.05 to 1, 5 wt .-%, particularly preferably 0.1 to 1 wt .-%, most preferably 0.3 to 0.6 wt .-%, each based on Monomer a). As the crosslinker content increases, the centrifuge retention capacity (CRC) decreases and the absorption increases under a pressure of 0.3 psi

(AUL0.3 psi).

As initiators c) it is possible to use all compounds which generate radicals under the polymerization conditions, for example thermal initiators, redox initiators, photoinitiators. Suitable redox initiators are sodium peroxodisulfate / ascorbic acid, hydrogen peroxide / ascorbic acid, sodium peroxodisulfate / sodium bisulfite and hydrogen peroxide / sodium bisulfite. Preference is given to using mixtures of thermal initiators and redox initiators, such as sodium peroxodisulfate / hydrogen peroxide / ascorbic acid. The reducing component but is preferably the mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid described in greater detail below, the acid disodium salt of 2-hydroxy-2-sulfonatoessig- and sodium bisulfite (Brüggolit ^® FF6M or Brüggolit ^® FF7).

Examples of suitable ethylenically unsaturated monomers d) which can be copolymerized with the ethylenically unsaturated monomers having acid groups are acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, Dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, maleic acid or its salts and maleic anhydride.

As water-soluble polymers e) it is possible to use polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, modified cellulose, such as methylcellulose or hydroxyethylcellulose, gelatin, polyglycols or polyacrylic acids, preferably starch, starch derivatives and modified cellulose.

Usually, an aqueous monomer solution is used. The water content of the monomer solution is preferably from 40 to 75 wt .-%, particularly preferably from 45 to 70 wt .-%, most preferably from 50 to 65 wt .-%. It is also possible monomer suspensions, i. to use supersaturated monomer solutions. With increasing water content, the energy expenditure increases during the subsequent drying and with decreasing water content, the heat of polymerization can only be sufficiently dissipated.

Optionally, at least one water-soluble alkaline earth salt selected from the salts of calcium, strontium or barium is added to the superabsorbent according to the invention. Mixtures of salts of all possible combinations of two of these elements or all three of these elements can be used. In the technical effect, there is no significant difference between the salts of calcium, strontium or barium, but for economic reasons, calcium salts are usually preferred. In general, with alkaline earth salt-containing superabsorbent, a smaller amount of stabilizers according to the invention is necessary against discoloration than without alkaline earth salt.

The anions of the alkaline earth salts can basically be chosen freely, with the restriction that they must not lead to negative effects in the superabsorber and / or in its application. Examples of suitable anions of the alkaline earth metal salts are halides, in particular chloride, hydroxide, carbonate, carboxylate, such as formate, acetate, propionate or lactate, nitrate or sulfate. Mixtures can also be used.

Preferably, water-soluble alkaline earth salts are used or those which, although themselves relatively poorly soluble in water, react rapidly with the acid groups of the superabsorbent or the monomers. Such salts have the advantage, in particular in the customary preparation of the superabsorber from water-containing monomer mixtures, that an equivalent amount of the neutralizing agent otherwise used can be saved. The anions of the alkaline earth metal salt are selected accordingly, preference is given to hydroxide, carbonate or lactate. Total preferred alkaline earth salts are calcium hydroxide, strontium hydroxide, barium hydroxide, calcium carbonate, strontium carbonate, barium carbonate, calcium lactate, strontium lactate, barium lactate, calcium sulfate, strontium sulfate, barium sulfate or mixtures thereof. Particularly preferred are calcium hydroxide, calcium carbonate, calcium lactate and calcium sulfate.

The alkaline earth salt is generally used in an amount of at least 0.1% by weight, preferably at least 0.5% by weight and more preferably at least 1% by weight and generally at most 20% by weight, preferably at most 10 wt .-% and in a particularly preferred form of at most 5 wt .-% added, in each case based on the total amount of ethylenically unsaturated, at least one acid group-carrying monomers. These are calculated as free acid, any total or partial neutralization of the acid groups is not taken into account in the calculation. Some alkaline earth salts may contain water of crystallization. This is also not taken into account in the calculation.

The alkaline earth salt (or mixture of alkaline earth salts) is added to the monomer mixture before or during the polymerization or, if the polymerization is followed by a separate drying step, to the polymer before drying, or partially before or during the polymerization and partly to the polymer before drying. The aim is a uniform distribution of the alkaline earth salt in the superabsorbent. Basically, the alkaline earth salt is mixed by method and time as described below for the neutralizing agent. The simplest and therefore preferred is the addition into the monomer mixture before the polymerization. However, the alkaline earth metal salt can also be introduced into the resulting polymer gel during the polymerization or after the polymerization, but it is in any case introduced before the drying. The addition during the polymerization is particularly easy in the methods in which the polymerizing composition is mixed, for example, in polymerization in a kneader. The addition after the polymerization and before the drying is easy, above all, in the processes in which the polymerized mass from the polymerization is passed into a separate drying step, ie in particular in all processes in which polymerization and drying are carried out in separate apparatuses become. The alkaline earth salt may in this case be mixed into the polymer gel by any known mixing method and apparatus.

The alkaline earth salt is added as a dry substance or as a solution or dispersion in a solvent. The solvent used is preferably water.

The preferred polymerization inhibitors require dissolved oxygen for optimum performance. Therefore, the monomer solution can be freed of dissolved oxygen prior to the polymerization by inertization, ie by flowing through with an inert gas, preferably nitrogen or carbon dioxide. Preferably, the oxygen the monomer solution before polymerization to less than 1 ppm by weight, more preferably to less than 0.5 ppm by weight, most preferably to less than 0.1 ppm by weight, lowered. The monomer mixture may contain other components. Examples of other components used in such monomer mixtures include chelating agents to keep metal ions in solution.

The acid groups of the polymer gels obtained from the polymerization are usually partially neutralized. The neutralization is preferably carried out at the stage of the monomers, in other words salts of the acid group-carrying monomers or, strictly speaking, a mixture of acid group-carrying monomers and salts of the acid group-carrying monomers ("partially neutralized acid") as component a) in the polymerization This is usually done by mixing the neutralizing agent as an aqueous solution or preferably also as a solid in the monomer mixture intended for the polymerization or preferably in the acid group-carrying monomer or a solution thereof The degree of neutralization is preferably from 25 to 95 mol%, particularly preferably from 50 to 80 mol%, very particularly preferably from 65 to 72 mol%, it being possible to use the customary neutralizing agents, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof ammonium salts can also be used. Sodium and potassium are particularly preferred as alkali metals, but very particularly preferred are sodium hydroxide, sodium carbonate or Natriumhydro- genkarbonat and mixtures thereof.

But it is also possible to carry out the neutralization after the polymerization at the stage of Polymergeis formed during the polymerization. Furthermore, it is possible to neutralize up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, of the acid groups before the polymerization by adding a part of the neutralizing agent already to the monomer solution and the desired final degree of neutralization only after the polymerization is adjusted at the stage of Polymergeis. If the polymer gel is at least partially neutralized after the polymerization, the polymer gel is preferably comminuted mechanically, for example by means of an extruder, wherein the neutralizing agent can be sprayed, sprinkled or poured on and then thoroughly mixed in. For this purpose, the gel mass obtained can be extruded several times for homogenization.

However, it is preferred to carry out the neutralization at the stage of the monomer. In other words, in a very particularly preferred embodiment, the monomer a) used is a mixture of from 25 to 95 mol%, particularly preferably from 50 to 80 mol%. , very particularly preferably from 65 to 72 mol% salt of the acid group carrier the monomers and the remainder used to 100 mol% acid group-carrying monomer. This mixture is, for example, a mixture of sodium acrylate and acrylic acid or a mixture of potassium acrylate and acrylic acid. In a preferred embodiment, a neutralizing agent is used for neutralization, the content of iron is generally below 10 ppm by weight, preferably below 2 ppm by weight and most preferably below 1 ppm by weight. Similarly, a low content of chloride and anions of oxygen acids of the chlorine is desired. A suitable neutralizing agent is, for example, the 50% strength by weight sodium hydroxide solution or potassium hydroxide solution, which is usually sold as "membrane grade", even purer and equally suitable, but also more expensive is the 50% by weight conventionally sold as "amalgam grade" or "mercury process". % sodium hydroxide solution or potassium hydroxide solution.

If, in the optional embodiment of the invention in which an alkaline earth salt is added, the alkaline earth salt used is a water-soluble or a relatively poorly soluble, yet relatively fast-reacting alkaline earth metal salt, the amount of neutralizing agent added can be reduced by adding an amount of alkaline earth metal ions. In other words, the alkaline earth salt may also serve as a neutralizing agent at the same time, the divalent alkaline earth ion replacing two monovalent alkali ions. For this purpose, in particular alkaline earth metal hydroxides, carbonates and lactates are suitable.

Also, processes for producing superabsorbents from monomer mixtures such as those exemplified above are known. Suitable polymerization reactors are, for example, kneading reactors or belt reactors. In the kneader, the polymer gel formed in the polymerization of an aqueous monomer solution or suspension is comminuted continuously by, for example, counter-rotating stirring shafts, as described in WO 2001/38402 A1. The polymerization on the belt is described, for example, in EP 955 086 A2, DE 38 25 366 A1 and US Pat. No. 6,241,928. During polymerization in a belt reactor, as in the case of the likewise known polymerization in batch operation or in the tubular reactor, as described, for example, in EP 445 619 A2 and DE 19 846 413 A1, a polymer gel must be comminuted in a further process step, for example in one Meat grinder, extruder or kneader. However, it is also possible to produce spherical or differently shaped superabsorbent particles by suspension or emulsion polymerization, as described, for example, in EP 457 660 A1, or by spray or drop polymerization processes, as for example in EP 348 180 A1, EP 816 383 A1, WO 96 404 27 A1, US Pat. No. 4,020,256, US 2002/0 193 546 A1, DE 35 19 013 A1, DE 10 2005 044 035 A1, WO 2007/093531 A1, WO 2008/086 976 A1 or US Pat

WO 2009/027 356 A1. Also known are methods in which the monomer mixture is applied to a substrate such as a nonwoven web and polymerized, as described for example in WO 02/94 328 A2 and WO 02/94 329 A1. The polymer gel obtained from the aqueous solution polymerization and optionally subsequent neutralization is then preferably dried with a belt dryer until the residual moisture content is preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-%, most preferably 2 to 8 wt .-%, is (measurement method for the residual moisture or water content, see below). If the residual moisture content is too high, the dried polymer gel has too low a glass transition temperature Tg and is difficult to process further. If the residual moisture content is too low, the dried polymer gel is too brittle and in the subsequent comminution steps undesirably large amounts of polymer particles with too small particle size ("fines") are produced. %, preferably from 30 to 80 wt .-%, particularly preferably from 35 to 70 wt .-%, most preferably from 40 to 60 wt .-%. Optionally, for drying but also a fluidized bed dryer or a heatable mixer with mechanical mixing element Optionally, the dryer may be operated under nitrogen or other non-oxidizing inert gas, or at least a reduced partial pressure of oxygen to prevent oxidative yellowing, but usually results in a drier or similar dryer also adequate ventilation and drainage of the water steam to an acceptable product. Advantageous in terms of color and product quality is usually the shortest possible drying time.

During drying, the residual monomer content in the polymer particles also decreases and the last residues of the initiator are destroyed.

The dried polymer gel is then ground and classified, wherein for grinding usually one- or multi-stage roller mills, preferably two- or three-stage roller mills, pin mills, hammer mills or vibratory mills can be used. Oversized gel lumps, often not dried on the inside, are rubber-elastic, cause grinding problems and are preferably used before grinding

Grind separation, which can be done easily by air classification or a sieve ("protective sieve" for the mill) .The mesh size of the sieve is to be chosen in view of the mill used so that as possible no interference from oversized, rubbery particles occur.

Too large, insufficiently finely ground superabsorbent particles are in their overwhelming use, in hygiene products such as diapers, as coarse particles perceptible, they also reduce the average swelling rate of the superabsorbent Both is undesirable. Advantageously, therefore, coarse-grained polymer particles are separated from the product. This is done by conventional classification methods, such as air classification or sieving through a sieve with a mesh size of at most 1000 μηη, preferably at most 900 μηη, more preferably at most 850 μηι and most preferably at most 800 μηι. For example, screens are used with 700 μηη, 650 μηη or 600 μηη mesh size. The separated coarse-grained polymer particles ("oversize") can be fed back to the grinding and screening circuit for cost optimization or further processed separately.

Polymer particles with too small particle size lower the permeability (SFC). Advantageously, therefore, also fine-grained polymer particles are separated in this classification. This can, if sieved, conveniently by a sieve with a mesh size of at most 300 μηη, preferably at most 200 μηη, more preferably used at most 150 μηη and most preferably not more than 100 μηη. The separated fine-grained polymer particles ("undersize" or "fines") can be fed back to the monomer stream, the polymerizing gel, or the polymerized gel before drying the gel for cost optimization.

The mean particle size of the polymer particles separated off as product fraction is generally at least 200 μm, preferably at least 250 μm, and preferably at least 300 μm, and generally at most 600 μm, and more preferably at most 500 μm. The proportion of particles having a particle size of at least 150 μm is generally at least 90% by weight, preferably at least 95% by weight and most preferably at least 98% by weight. The proportion of particles with a particle size of at most 850 μm, is generally at least 90% by weight, preferably at least 95% by weight and more preferably at least 98% by weight.

In some other known production processes for superabsorbents, in particular in suspension polymerization, spray or dropletization polymerization, the particle size distribution is predetermined by the choice of process parameters. In these processes, particulate superabsorbents of the desired particle size are formed directly, so that milling and screening steps can often be omitted. In some processes (in particular in the case of spray or dropletization polymerization), a separate drying step can often be dispensed with.

The polymer produced in this way has superabsorbent properties and is referred to as "superabsorbent." Its CRC is typically comparatively high, while its AUL or SFC is comparatively low. Called base polymer "or" base polymer ".

Suitable postcrosslinkers are compounds which contain groups which can form bonds with at least two functional groups of the superabsorbent particles. Acrylic acid / sodium acrylate-based superabsorbents which are prevalent on the market are suitable surface postcrosslinker compounds which contain groups which can form bonds with at least two carboxylate groups. Preferred postcrosslinkers are amide acetals or carbamates of the general formula (I)

worin R¹ Ci-Ci2-Alkyl, C₂-Ci₂-Hydroxyalkyl, C₂-Ci₂-Alkenyl oder C₆-Ci₂-Aryl,

wherein R ¹ is Ci-Ci2-alkyl, C ₂ -C ₂ hydroxyalkyl, C ₂ -C ₂ -alkenyl or C ₆ -C ₂ aryl,

R ² X or OR ⁶ '

R ³ is hydrogen, Ci-Ci ₂ -alkyl, C ₂ -C ₂ hydroxyalkyl, C ₂ -C ₂ -alkenyl or C ₆ -C ₂ aryl, or X,

R ⁴ Ci-Ci ₂ -alkyl, C ₂ -C ₂ hydroxyalkyl, C ₂ -C ₂ -alkenyl or C ₆ -C ₂ aryl,

R ⁵ is hydrogen, Ci-Ci ₂ -alkyl, C ₂ -C ₂ hydroxyalkyl, C ₂ -C ₂ -alkenyl, _Ci-Ci2 acyl or

R ⁶ Ci-Ci ₂ -alkyl, C ₂ -C ₂ hydroxyalkyl, C ₂ -C ₂ -alkenyl or C ₆ -C ₂ aryl, and

X is a carbonyl oxygen common to the radicals R ² and R ³ , where R ¹ and R ⁴ and / or R ⁵ and R ^{6 may be} a bridged C ₂ -C ⁶ alkanediyl, and where the abovementioned radicals R ¹ to R ^{6 are} still may have at least one to two free valences and may be connected to these free valencies with at least one suitable base, or polyhydric alcohols, wherein the polyhydric alcohol preferably has a molecular weight of less than 100 g / mol, preferably less than 90 g / mol , more preferably less than 80 g / mol, most preferably less than 70 g / mol, per hydroxy group and no vicinal, geminal, secondary or tertiary hydroxy groups, and polyhydric alcohols either diols of general formula (IIa) HO R ⁷ - OH (IIa) where R ^{7 is} either an unbranched alkylene radical of the formula - (CH 2) _n -, where n is an integer from 3 to 20, preferably 3 to 12, and both hydroxy groups are terminal, or R ⁷ denotes an unbranched, branched or cyclic alkylene radical, or polyols of the general formula (IIb)

worin die Reste R⁸, R⁹, R¹⁰, R¹¹ unabhängig voneinander Wasserstoff, Hydroxyl, Hydroxymethyl, Hydroxyethyloxymethyl, 1 -Hydroxyprop-2-yloxymethyl, 2- Hydroxypropyloxymethyl, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, n-Pentyl, n-Hexyl, 1 ,2-Dihydroxyethyl, 2-Hydroxyethyl, 3-Hydroxypropyl oder 4-Hydroxybutyl bedeuten und insgesamt 2, 3, oder 4, bevorzugt 2 oder 3, Hydroxygruppen vorhanden sind, und nicht mehr als einer der Reste R⁸, R⁹, R¹⁰, oder R¹¹ gleich Hydroxyl bedeutet, sind, oder cyclische Carbonate der allgemeinen Formel (III)

in which the radicals R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ independently of one another denote hydrogen, hydroxyl, hydroxymethyl, hydroxyethyloxymethyl, 1-hydroxyprop-2-yloxymethyl, 2-hydroxypropyloxymethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, 1, 2-dihydroxyethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl and a total of 2, 3, or 4, preferably 2 or 3, hydroxy groups are present, and not more than one of R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ is hydroxyl, are, or cyclic carbonates of the general formula (III)

worin R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ und R¹⁷ unabhängig voneinander Wasserstoff, Methyl, E- thyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl oder Isobutyl, und n entweder 0 oder 1 ist, oder Bisoxazoline der allgemeinen Formel (IV)

worin R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴ und R²⁵ unabhängig voneinander Wasserstoff, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl oder Isobutyl, und R²⁶ eine Ein- fachbindung, einen linearen, verzweigten oder cyclischen C2-Ci2-Alkylenrest, oder einen Polyalkoxydiylrest darstellt, welcher aus ein bis zehn Ethylenoxid- und/oder Propy- lenoxideinheiten aufgebaut ist, wie sie beispielsweise Polyglykoldicarbonsäuren aufweisen. Bevorzugte Nachvernetzer der allgemeinen Formel (I) sind 2-Oxazolidone, wie 2- Oxazolidon und N-(2-Hydroxyethyl)-2-oxazolidon, N-Methyl-2-Oxazolidon, N-Acyl-2- oxazolidone, wie N-Acetyl-2-oxazolidon, 2-Oxotetrahydro-1 ,3-oxazin, bicyclische Ami- dacetale, wie 5-Methyl-1 -aza-4,6-dioxa-bicyclo[3.3.0]octan, 1 -Aza-4,6-dioxa- bicyclo[3.3.0]octan und 5-lsopropyl-1 -aza-4,6-dioxa-bicyclo [3.3.0] octan, Bis-2- oxazolidone und Poly-2-oxazolidone.

wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^{17 are} independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl, and n is either 0 or Is 1, or bisoxazolines of the general formula (IV)

wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ^{25 are} independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl, and R ^{26 represents} a single bond, a linear, branched or cyclic C 2 -C 12 -alkylene radical, or a polyalkoxydiyl radical which is composed of one to ten ethylene oxide and / or propylene oxide units, such as, for example, polyglycol dicarboxylic acids. Preferred postcrosslinkers of the general formula (I) are 2-oxazolidones, such as 2-oxazolidone and N- (2-hydroxyethyl) -2-oxazolidone, N-methyl-2-oxazolidone, N-acyl-2-oxazolidones, such as N-acetyl -2-oxazolidone, 2-oxotetrahydro-1,3-oxazine, bicyclic amidacetals such as 5-methyl-1 -aza-4,6-dioxa-bicyclo [3.3.0] octane, 1-aza-4,6 -dioxabicyclo [3.3.0] octane and 5-isopropyl-1 -aza-4,6-dioxa-bicyclo [3.3.0] octane, bis-2-oxazolidones and poly-2-oxazolidones.

Particularly preferred postcrosslinkers of the general formula (I) are 2-oxazolidone, N-methyl-2-oxazolidone, N- (2-hydroxyethyl) -2-oxazolidone and N-hydroxypropyl-2-oxazolidone.

Preferred postcrosslinkers of the general formula (IIa) are 1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 7-heptanediol. Further examples of postcrosslinkers of the formula (IIa) are 1, 3-butanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol. The diols are preferably water-soluble, wherein the diols of the general formula (IIa) at 23 ° C to at least 30 wt .-%, preferably at least 40 wt .-%, particularly preferably at least 50 wt .-%, most preferably at least 60 wt .-%, in water, such as 1, 3-propanediol and 1, 7-heptanediol. Even more preferred are those postcrosslinkers which are liquid at 25 ° C.

Preferred postcrosslinkers of the general formula (IIb) are butane-1, 2,3-triol, butane-1, 2,4-triol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, per molecule 1 to 3 times ethoxylated glycerol, trimethylolethane or Trimethylolpropane and per molecule 1 - to 3-fold propoxylated glycerol, trimethylolethane or trimethylolpropane. Also preferred are 2-fold ethoxylated or propoxylated neopentyl glycol. Particularly preferred are 2-fold and 3-fold ethoxylated glycerol, neopentyl glycol, 2- Methyl 1, 3-propanediol and trimethylolpropane.

Preferred polyhydric alcohols (IIa) and (IIb) have a viscosity at 23 ° C. of less than 3000 mPas, preferably less than 1500 mPas, preferably less than 1000 mPas, more preferably less than 500 mPas, very particularly preferably less than 300 mPas, on.

Particularly preferred postcrosslinkers of the general formula (III) are ethylene carbonate and propylene carbonate.

A particularly preferred postcrosslinker of the general formula (IV) is 2,2'-bis (2-oxazoline).

The preferred postcrosslinkers minimize side reactions and subsequent reactions which lead to volatile and thus malodorous compounds. The superabsorbers produced with the preferred postcrosslinkers are therefore odorless even when moistened.

It is possible to use a single postcrosslinker from the above selection or any mixtures of different postcrosslinkers.

The postcrosslinker is generally used in an amount of at least 0.001% by weight, preferably at least 0.02% by weight, more preferably at least 0.05% by weight, and generally at most 2% by weight, preferably at most 1% by weight, in a particularly preferred form at most 0.3% by weight, for example at most 0.15% by weight or at most 0.095% by weight, in each case based on the mass of the base polymer (for example the relevant Sieve fraction). The postcrosslinking is usually carried out by spraying a solution of the postcrosslinker onto the dried base polymer particles. Subsequent to the spraying, the polymer particles coated with postcrosslinker are thermally dried, wherein the postcrosslinking reaction can take place both before and during the drying. If surface postcrosslinkers with polymerizable groups are used, the surface postcrosslinking can also be effected by free-radically induced polymerization of such groups by means of conventional free-radical formers or else by means of high-energy radiation such as UV light. This can be done in parallel or instead of using postcrosslinkers that form covalent or ionic bonds to functional groups on the surface of the base polymer particles. The spraying of Nachvernetzerlösung is preferably carried out in mixers with moving mixing tools, such as screw mixers, disc, paddle or paddle mixers or mixers with other mixing tools. However, particularly preferred are vertical mixers. However, it is also possible to spray the postcrosslinker solution in a fluidized bed. Suitable mixers are flocking for example as a plow mixer ^® Gebr Lödige Maschinenbau GmbH, Elsener Street. 7 - 9, 33102 Paderborn, Germany, or ^® as Schugi ^® Flexomix mixer, Vrieco-Nauta ^® mixer or blender Turbulizer® ^® from Hosokawa Micron BV, Gildenstraat 26, 7000 AB Doetinchem, The Netherlands.

The applicable spray nozzles are subject to no restriction. Suitable nozzles and atomization systems are described, for example, in the following references: Atomization of Liquids, Expert-Verlag, Vol. 660, series Kontakt & Studium, Thomas Richter (2004) and in atomization technology, Springer-Verlag, VDI series, Günter Wozniak (2002 ). Applicable are mono- and polydisperse spray systems. Among the polydisperse systems are single-fluid pressure nozzles (jet or lamella-forming), rotary atomizers, two-component atomizers, ultrasonic atomizers and impact nozzles. In the two-component atomizers, the mixture of the liquid and the gas phase can take place both internally and externally. The spray pattern of the nozzles is not critical and can take any shape, such as omnidirectional, fan-beam, wide-angle omnidirectional or circular ring spray pattern. It is advantageous to use a non-oxidizing gas, if two-component atomizers are used, particularly preferably nitrogen, argon or carbon dioxide. Such nozzles, the liquid to be sprayed can be supplied under pressure. The division of the liquid to be sprayed can take place in that it is relaxed after reaching a certain minimum speed in the nozzle bore. Furthermore, single-substance nozzles, such as, for example, slot nozzles or twist chambers (full-cone nozzles) can also be used for the purpose according to the invention (for example, by Düsen-Schlick GmbH, DE, or by Spraying Systems Deutschland GmbH, DE). Such nozzles are also described in EP 0 534 228 A1 and EP 1 191 051 A2.

The postcrosslinkers are typically used as an aqueous solution. If only water is used as the solvent, the postcrosslinker solution or the base polymer is advantageously added with a surfactant or deagglomerization aid. This improves the wetting behavior and reduces the tendency to clog.

All anionic, cationic, nonionic and amphoteric surfactants are suitable as Deagglomerationshilfsmittel, but are preferred for skin compatibility reasons non-ionic and amphoteric surfactants. The surfactant may also contain nitrogen. For example, sorbitan monoesters such as sorbitan monococoate and sorbitan tanmonolaurate, or ethoxylated variants thereof, such as polysorbate 20 ^® added. Other suitable deagglomerating assistants the ethoxylated and alkoxylated derivatives of 2-propylheptanol, which are marketed under the brand names Lutensol® XL ^® and Lutensol XP ^® (BASF SE, Carl-Bosch-Straße 38, 67056 Ludwigshafen hafen, Germany).

The Deagglomerationshilfsmittel can be metered separately or the Nachvernetzerlosung be added. Preferably, the deagglomerating aid is simply added to the postcrosslinker solution.

The amount used of the deagglomerating assistant based on the base polymer is, for example, 0 to 0.1% by weight, preferably 0 to 0.01% by weight, particularly preferably 0 to 0.002% by weight. Preferably, the deagglomerating aid is metered so that the surface tension of an aqueous extract of the swollen base polymer and / or the swollen postcrosslinked water-absorbing polymer at 23 ° C at least 0.060 N / m, preferably at least 0.062 N / m, more preferably at least 0.065 N / m, and advantageously not more than 0.072 N / m. The aqueous Nachvernetzerlosung may also contain a cosolvent in addition to the at least one postcrosslinker. About the content of non-aqueous solvent or total solvent amount, the penetration depth of the postcrosslinker can be adjusted in the polymer particles. Technically suitable cosolvents are C 1 -C 6 -alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or 2-methyl-1-propanol, C 2 -C 5 -diols, such as Ethylene glycol, 1, 2

Propylene glycol or 1, 4-butanediol, ketones, such as acetone, or carboxylic acid esters, such as ethyl acetate. A disadvantage of some of these cosolvents is that they have typical odors. The co-solvent itself is ideally not a postcrosslinker under the reaction conditions. However, in the limiting case and depending on residence time and temperature, it may happen that the cosolvent partially contributes to crosslinking. This is particularly the case when the postcrosslinker is relatively inert and therefore can itself form its cosolvent, such as when using cyclic carbonates of the general formula (III), diols of the general formula (IIa) or polyols of the general formula (IIb) , Such postcrosslinkers can also be used as cosolvents in a mixture with more reactive secondary crosslinkers since the actual postcrosslinking reaction can then be carried out at lower temperatures and / or shorter residence times than in the absence of the more reactive crosslinker. Since co-solvent is used in relatively large amounts and also remains partially in the product, it must not be toxic. In the process according to the invention, the diols of the general formula (IIa), the polyols of the general formula (IIb) and the cyclic carbonates of the general formula (III) are also suitable as cosolvents. They fulfill this function in the presence of a reactive postcrosslinker of the general formula (I) and / or (IV) and / or a di- or triglycidyl compound. However, preferred cosolvents in the process according to the invention are, in particular, the diols of the general formula (IIa), especially when the hydroxyl groups are hindered sterically by neighboring groups on a reaction. Although such diols are in principle also suitable as postcrosslinkers, they require significantly higher reaction temperatures or optionally higher amounts of use than sterically unhindered diols.

Particularly preferred combinations of less reactive postcrosslinker as cosolvent and reactive postcrosslinker are combinations of preferred polyhydric alcohols, diols of general formula (IIa) and polyols of general formula (IIb), with amide acetals or carbamates of general formula (I).

Suitable combinations are, for example, 2-oxazolidone / 1, 2-propanediol and N- (2-hydroxyethyl) -2-oxazolidone / 1, 2-propanediol and ethylene glycol diglycidyl ether / 1, 2-propanediol.

Very particularly preferred combinations are 2-oxazolidone / 1,3-propanediol and N- (2-hydroxyethyl) -2-oxazolidone / 1,3-propanediol.

Further preferred combinations are those with ethylene glycol diglycidyl ether or glycerol or triglycidyl ether with the following solvents, cosolvents or co-crosslinkers: isopropanol, 1,3-propanediol, 1,2-propylene glycol or mixtures thereof.

Further preferred combinations are those with 2-oxazolidone or (2-hydroxyethyl) -2-oxazolidone in the following solvents, cosolvents or co-crosslinkers: isopropanol, 1, 3-propanediol, 1, 2-propylene glycol, ethylene carbonate, propylene carbonate or mixtures thereof.

Frequently, the concentration of cosolvent in the aqueous postcrosslinker solution is from 15 to 50% by weight, preferably from 15 to 40% by weight, more preferably from 20 to 35% by weight, based on the postcrosslinker solution. For cosolvents which are only slightly miscible with water, it is advantageous to adjust the aqueous postcrosslinker solution so that only one phase is present, if appropriate by lowering the concentration of the cosolvent. In a preferred embodiment, no cosolvent is used. The postcrosslinker is then used only as a solution in water, optionally with the addition of a deagglomerating auxiliary. The concentration of the at least one postcrosslinker in the aqueous postcrosslinker solution is typically from 1 to 20% by weight, preferably from 1 to 5% by weight, particularly preferably from 2 to 5% by weight, based on the postcrosslinker solution.

The total amount of Nachvernetzerlosung based on the base polymer is usually from 0.3 to 15 wt .-%, preferably from 2 to 6 wt .-%.

The actual surface postcrosslinking by reaction of the surface postcrosslinker with functional groups on the surface of the base polymer particles is usually carried out by heating the base polymer wetted with surface postcrosslinker solution, usually called "drying" (but not to be confused with the above-described drying of the polymer gel from the polymerization) The drying can be carried out in the mixer itself, by heating the jacket, by heat exchange surfaces or by blowing warm gases in. Simultaneous addition of the superabsorbent with surface postcrosslinker and drying can take place, for example, in a fluidized-bed dryer but is usually carried out in a downstream dryer, such as a hopper dryer, a rotary kiln, a paddle or disc dryer or a heated screw ielsweise as Solidair ^® or Torusdisc ^® -T Rockner from Bepex International LLC, 333 NE Taft Street, Minneapolis, MN 55413, USA, or as a paddle or paddle dryer or as a fluidized bed dryer of Nara Machinery Co., Ltd., branch Europa, Europa Allee 46, 50226 Frechen, Germany available.

It is possible to heat the polymer particles for drying and carrying out the surface postcrosslinking via contact surfaces in a downstream dryer, or via supplied warm inert gas, or via a mixture of one or more inert gases with water vapor, or only with steam alone. When the heat is supplied via contact surfaces, it is possible to carry out the reaction under slight or complete underpressure under inert gas. When steam is used for directly heating the polymer particles, it is desirable according to the invention to operate the dryer at normal pressure or overpressure. In this case, it may be useful to split the postcrosslinking step into a heating step with water vapor and a reaction step under inert gas but without water vapor. This can be realized in one or more apparatuses. According to the invention, the polymer particles can already be heated in the post-crosslinking mixer with steam. The base polymer used may still have a temperature of 10 to 120 ° C from previous process steps, the Nachvernetzerlosung may have a temperature of 0 to 70 ° C. In particular, the postcrosslinker solution can be heated to reduce the viscosity. Preferred drying temperatures are in the range 100 to 250 ° C, preferably 120 to 220 ° C, more preferably 130 to 210 ° C, most preferably 150 to 200 ° C. The preferred residence time at this temperature in the reaction mixer or dryer is preferably at least 10 minutes, more preferably at least 20 minutes, most preferably at least 30 minutes, and usually at most 60 minutes. Typically, the drying is conducted in such a way that the superabsorber has a residual moisture content of generally at least 0.1% by weight, preferably at least 0.2% by weight and in a particularly preferred form at least 0.5% by weight, and also Generally at most 15% by weight, preferably at most 10% by weight and in a particularly preferred form at most 8% by weight.

Postcrosslinking can take place under normal atmospheric conditions. Normal atmospheric conditions means that no technical precautions are taken to reduce the partial pressure of oxidizing gases such as atmospheric oxygen in the apparatus in which the postcrosslinking reaction predominantly takes place (the "postcrosslinking reactor", typically the dryer), but it is preferred Oxidizing gases are substances which have a vapor pressure of at least 1013 mbar at 23 ° C. and act as oxidizing agents in combustion processes, for example oxygen, nitrogen oxide and nitrogen dioxide, in particular oxygen less than 140 mbar, preferably less than 100 mbar, particularly preferably less than 50 mbar, very particularly preferably less than 10 mbar, if the thermal postcrosslinking is carried out at ambient pressure, ie at a total pressure of around 1013 mbar, Thus, the total partial pressure of the oxidizing gases is determined by their volume fraction. The proportion of oxidizing gases is preferably less than 14% by volume, preferably less than 10% by volume, particularly preferably less than 5% by volume, very particularly preferably less than 1% by volume. The post-crosslinking can be carried out under reduced pressure, ie at a total pressure of less than 1013 mbar. The total pressure is typically less than 670 mbar, preferably less than 480 mbar, more preferably less than 300 mbar, most preferably less than 200 mbar. If drying and postcrosslinking are carried out under air with an oxygen content of 20.8% by volume, the oxygen partial pressures corresponding to the abovementioned total pressures are 139 mbar (670 mbar), 100 mbar (480 mbar), 62 mbar (300 mbar) and 42 m mbar (200 mbar), with the respective total pressures in parentheses. Another way to reduce the partial pressure of oxidizing gases, the introduction of non-oxidizing gases, especially inert gases in the apparatus used for post-crosslinking. Suitable inert gases are gaseous substances at the postcrosslinking temperature and given pressure in the postcrosslinking dryer which, under these conditions, do not oxidize to the constituents of the drying polymer particles, for example nitrogen, carbon dioxide, argon, water vapor, with nitrogen being preferred. The amount of inert gas is generally from 0.0001 to 10 m ³ , preferably from 0.001 to 5 m ³ , more preferably from 0.005 to 1 m ³ , and most preferably from 0.005 to 0.1 m ³ , based on 1 kg of superabsorbent.

In the process according to the invention, the inert gas, if it does not contain water vapor, can be injected via nozzles into the postcrosslinking dryer, more preferably the inert gas is added to the polymer particle stream via nozzles via the nozzles in or just before the mixer by adding superoxide absorber with surface postcrosslinker ,

Of course, vapors of cosolvents removed from the dryer can be condensed outside the dryer again and, if necessary, recycled. In a preferred embodiment of the present invention, polyvalent cations are applied to the particle surface in addition to the postcrosslinkers before, during or after the postcrosslinking. This is in principle a further surface postcrosslinking by ionic, noncovalent bonds, but is sometimes also referred to as "complexing" with the metal ions in question or simply as "coating" with the relevant substances (the "complexing agent").

Polyvalent cations are applied by spraying solutions of divalent or polyvalent cations, usually divalent, trivalent or tetravalent metal cations, but also polyvalent cations, such as formally wholly or partly of vinylamine monomers, such as partially or completely hydrolyzed polyvinylamide ( Examples of divalent metal cations which may be used are, in particular, the divalent cations of metals of groups 2 (in particular Mg, Ca, Sr, Ba), 7 (in particular Mn), 8 (in particular Fe), 9 (in particular Co), 10 (in particular Ni), 11 (in particular Cu) and 12 (in particular Zn) of the Periodic Table of the Elements Examples of trivalent metal cations which may be used are in particular the trivalent cations of Group 3 metals, including lanthanides (in particular Sc, Y, La, Ce), 8 (in particular Fe), 1 1 (in particular Au) and 13 (in particular Al) of the Periodic Table of the Elements. Examples of suitable tetravalent cations are, in particular, the tetravalent cations of metals of the lanthanides (in particular Ce) and of group 4 (in particular Ti, Zr, Hf) of the Periodic Table of the Elements. The metal cations can be used alone or mixed with each other. Particularly preferred is the use of trivalent metal cations. Very particularly preferred is the use of aluminum cations. Of the cited metal cations, all metal salts which have sufficient solubility in the solvent to be used are suitable. Particularly suitable are metal salts with weakly complexing anions such as chloride, nitrate and sulfate, hydrogen sulfate, carbonate, bicarbonate, nitrate, phosphate, hydrogen phosphate, or dihydrogen phosphate. Preferred are salts of mono- and dicarboxylic acids, hydroxy acids, keto acids and amino acids or basic salts. Examples of acetates, propionates, tartrates, maleates, citrates, lactates, malates and succinates are also preferred is the use of hydroxides. Particularly preferred is the use of 2-hydroxycarboxylic acid salts such as citrates and lactates. Examples of particularly preferred metal salts are alkali metal and alkaline earth metal aluminates and their hydrates, for example sodium aluminate and its hydrates, aluminum acetate, aluminum propionate, aluminum citrate and aluminum lactate.

The cations and salts mentioned can be used in pure form or as a mixture of different cations or salts. The salts of the two and / or trivalent metal cation used may contain further secondary constituents such as unneutralized carboxylic acid and / or alkali metal salts of the neutralized carboxylic acid. Preferred alkali metal salts are those of sodium, potassium and ammonium. They are typically used as an aqueous solution which is obtained by dissolving the solid salt in water, or is preferably produced directly as such, whereby optionally drying and purification steps are avoided. Advantageously, the hydrates of said salts can be used, which often dissolve faster in water than the anhydrous salts. The amount of metal salt used is generally at least 0.001 wt .-%, preferably at least 0.01 wt .-% and in a particularly preferred form at least 0.1 wt .-%, for example at least 0.4 wt .-% and generally at most 5 wt .-%, preferably at most 2.5 wt .-% and in a particularly preferred form at most 1 wt .-%, for example at most 0.7 wt .-% in each case based on the mass of the base polymer.

The salt of the trivalent metal cation can be used as a solution or suspension. As solvents for the metal salts, water, alcohols, DMF, DMSO and mixtures of these components can be used. Particularly preferred are water and water / alcohol mixtures such as water / methanol, water / 1, 2-propanediol and water / 1, 3-propanediol.

The treatment of the base polymer with solution of a divalent or polyvalent cation is carried out in the same way as with surface postcrosslinkers, including the drying step. Surface postcrosslinker and polyvalent cation can be sprayed in a common solution or as separate solutions. The spraying of the metal salt solution on the superabsorbent particles can be both before and after the surface postcrosslinking. In a particularly preferred method, the spraying of the metal salt solution in the same step is carried out by spraying the crosslinker solution, wherein both solutions are sprayed separately successively or simultaneously via two nozzles, or crosslinker and metal salt solution can be sprayed together via a nozzle ,

If a drying step is carried out after the surface postcrosslinking and / or treatment with complexing agent, it is advantageous, but not absolutely necessary, to cool the product after drying. The cooling can be continuous or discontinuous, conveniently the product is continuously conveyed to a dryer downstream cooler. Any apparatus known for removing heat from powdered solids may be used for this purpose, in particular any apparatus mentioned above as a drying apparatus, unless it is supplied with a heating medium but with a cooling medium, such as cooling water, so that over the walls and depending on the construction No heat is introduced into the superabsorber via the stirring elements or other heat exchange surfaces, but is removed therefrom. Preference is given to the use of coolers in which the product is moved, ie cooled mixers, for example blade coolers, disk coolers or paddle coolers. The superabsorbent can also be cooled in the fluidized bed by blowing in a cooled gas such as cold air. The conditions of the cooling are adjusted so that a superabsorbent is obtained with the temperature desired for further processing. Typically, an average residence time in the condenser of generally at least 1 minute, preferably at least 3 minutes and more preferably at least 5 minutes and generally at most 6 hours, preferably at most 2 hours and more preferably at most 1 hour is set and the cooling capacity is so in that the product obtained has a temperature of generally at least 0 ° C, preferably at least 10 ° C and more preferably at least 20 ° C and generally at most 100 ° C, preferably at most 80 ° C and most preferably at most 60 ° C.

The surface postcrosslinked superabsorbent is optionally ground and / or sieved in the usual way. Milling is typically not required here, but most often, the setting of the desired particle size distribution of the product, the screening of formed agglomerates or fine grain is appropriate. Agglomerates and fines are either discarded or preferably recycled to the process in a known manner and at the appropriate place; Agglomerates after comminution. The particle sizes desired for surface postcrosslinked superabsorbents are the same as for base polymers. Optionally, the superabsorbers according to the invention are provided with further additives which stabilize against discoloration.

Known such stabilizers against discoloration are, for example, derivatives of sulfinic acid. Particularly suitable derivatives of sulfinic acid are, for example, compounds of the following formula (V):

worin

wherein

 M represents a hydrogen atom, an ammonium ion, a monovalent metal ion or one equivalent of a divalent metal ion of Groups 1, 2, 8, 9, 10, 12 or 14 of the Periodic Table of the Elements;

R ^{27 is} OH or NR ³⁰ R ³¹ , wherein R ³⁰ and R ³¹ independently of one another are H or C 1 -C 6 -alkyl;

R ^{28 is} H or an alkyl, alkenyl, cycloalkyl or aryl group, this group optionally having 1, 2 or 3 substituents which are independently selected from C 1 -C 6 -alkyl, OH, O-C 1 -C 6 -alkyl, Alkyl, halogen and CF3; and

R ^{29 is} COOM, SO 3M, COR ³⁰ , CONR ³⁰ R ³¹ or COOR ³⁰ , wherein M, R ³⁰ and R ^{31 have} the meanings given above or, when R ^{28 is} aryl, which is optionally substituted as indicated above, also stands for H,

 Salts thereof or mixtures of such compounds and / or salts thereof.

In the above formula (V), alkyl represents straight-chain or branched alkyl groups which preferably have 1-6, in particular 1-4, carbon atoms. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, etc. The same applies to the alkyl groups in O-alkyl. Alkenyl represents straight-chain or branched alkenyl groups which preferably have 3-8 carbon atoms, in particular 3-6 carbon atoms. A preferred alkenyl group is the allyl group. Cycloalkyl is in particular C 1 -C 6 -cycloalkyl, with cyclopentyl and cyclohexyl being particularly preferred. Aryl (also in aralkyl) is preferably phenyl or naphthyl. When the aryl group is a phenyl group and is substituted, it preferably has two substituents. These are available in particular in the 2- and / or 4- position.

Halogen is F, Cl, Br and I, preferably Cl and Br. M is preferably an ammonium, alkali metal or one equivalent of an alkaline earth metal or zinc ion. Suitable alkali metal ions are in particular sodium and potassium ions, and suitable alkaline earth metal ions are, above all, magnesium, strontium and calcium ions.

R ²⁷ is preferably a hydroxy or amino group.

R ²⁸ is preferably a hydrogen atom or an alkyl or aryl group which may be substituted as above. It preferably has one or two hydroxyl and / or alkoxy substituents.

R ²⁹ is preferably either COOM or COOR ³⁰ (M and R ³⁰ have the meanings given above) or, when R ^{27 is} aryl, which may be substituted as indicated above, also for a hydrogen atom. In a preferred embodiment, the superabsorbent contains compounds of the above formula wherein M is an alkali metal ion or one equivalent of an alkaline earth metal or zinc ion; R ^{27 is} a hydroxy or amino group; R ^{28 is} H or alkyl and R ^{29 is} COOM or COOR ³⁰ , wherein when R ^{29 is} COOM, M in this COOM moiety is H, an alkali metal ion or an equivalent of an alkaline earth metal ion, and when R ^{29 is} COOR ³⁰ , R ^{30 is} Ci-C ₆ alkyl.

In another preferred embodiment, the superabsorbent contains compounds of the above formula wherein M is an alkali metal ion or one equivalent of an alkaline earth metal or zinc ion; R ^{27 is} a hydroxy or amino group; R ^{28 is} aryl which is optionally substituted as indicated above, in particular hydroxyphenyl or C 1 -C 4 alkoxyphenyl; and R ^{29 is} a hydrogen atom.

Groups 1 (H, Li, Na, K, Rb, Cs, Fr), 2 (Be, Mg, Ca, Sr, Ba, Ra), 8 (Fe, Ru, Os), 9 (Co, Rh, Ir ), 10 (Ni, Pd, Pt), 12 (Zn, Cd, Hg), and 14 (C, Si, Ge, Sn, Pb) of the periodic table of elements in the current IUPAC numbering (International Union of Pure and Applied Chemistry, 104 TW Alexander Drive, Building 19, Research Tri- angle Park, NC 27709, USA, www.iupac.org), the international nomenclature organization responsible for chemistry, corresponds to Groups Ia, IIa, IIb, IVa and VIIIb in the numbering used by CAS (Chemical Abstracts Service, 2540 Olentangy River Road, Columbus, OH 43202, USA, www.cas.org).

The sulfinic acid derivatives of the above formula can be used in pure form, but optionally also in the usual manner resulting from the preparation of such compounds with the sulfite of the corresponding metal ion and the corresponding sulfonic acid. The preparation of such sulfinic acid derivatives of the above formula is known and described for example in WO 99/18 067 A1. They are also common commodities and, for example, in the form of mixtures from the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite by L. Brüggemann KG (Salzstraße 131, 74076 Heilbronn, Germany, www.brueggemann.com) under the names BRÜGGOLIT ^® FF6M or BRÜGGOLIT ^® FF7, alternatively BRUGGOLITE ^® FF6M or BRUGGOLITE ^® FF7 available.

Optionally, the superabsorber according to the invention is also mixed with at least one inorganic water-insoluble particulate solid. Basically, any inorganic water-insoluble powder is suitable for this purpose. Examples are in general solid, chemically inert (that is, superabsorbent non-interfering) substances such as oxides, oxide hydroxides, hydroxides, sulfates, carbonates zeolites, inorganic pigments, minerals or clays. Examples are sulfates such as magnesium sulfate or barium sulfate, carbonates such as calcium carbonate, magnesium carbonate or dolomite, silicates such as calcium silicate or magnesium silicate, carbides such as perlite or silicon carbide, diatomaceous earth or fly ash.

Suitable oxides are the metal oxides of Groups 2 to 14 of the Periodic Table of the Elements, including the lanthanides and actinides. Examples of particularly suitable oxides are magnesium oxide, calcium oxide, strontium oxide, barium oxide, titanium dioxide, zirconium dioxide, vanadium oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese dioxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, boron oxide, aluminum oxide, silicon dioxide, tin oxide, lead oxide, lanthanum oxide or ceria. For clarification: The use of a trivial name for metal oxides should not be a statement about the valence of the metal and the stoichiometry of the oxide. If one element forms multiple oxides, generally all are suitable. In individual cases, the oxide is selected according to considerations specific to the individual case, for example by price, toxicity, stability or color. Examples of particularly suitable oxides are titanium dioxide, in particular in the anatase or rutile modifications, precipitated or pyrolysis-produced silicon dioxide.

Clays are silicates or aluminosilicates which are usually obtained by mining of natural sediments and occasionally also their further processing. However, some clays are made synthetically. It is also possible to use mixtures of these substances.

The inorganic water-insoluble solid is particulate, it is in powder form. The average particle size is typically in the range of at least 0.001 μηη, preferably at least 0.002 μηη, more preferably at least 0.005, and most preferably at least 0.01 μηη, and generally at most 500 μ, preferably at most 200 μηη, more preferably Form at most 100 μηη and in a very particularly preferred form of at most 50 μηι. The particles themselves may be aggregates or agglomerates of smaller primary particles. The particle size can be determined by means of sieve analysis, but it is simpler and therefore preferred to determine the particle size by means of laser diffraction technology. These methods are well known and routinely performed on suitable and commercially available equipment.

The aforementioned optional further anti-discoloration stabilizers and the inorganic water-insoluble particulate solid, when added, are generally present in amounts of at least 0.0001% by weight, preferably at least 0.001% by weight, and more preferably at least

0.025 wt .-% and generally at most 3 wt .-%, in a preferred form at most 2 wt .-% and in a particularly preferred form at most 0.5 wt .-% added, in each case based on the total weight of the superabsorbent according to the invention. In general, a lower amount of known stabilizers against discoloration is necessary with the alkaline earth salt-containing superabsorber according to the invention than without alkaline earth salt.

The mixture of superabsorbents with the stabilizers according to the invention to be used against discoloration, optional further stabilizers and the inorganic water-insoluble particulate solid can be carried out by any known mixing method. The anti-discoloration stabilizers to be used according to the invention, if in solid form, and the inorganic water-insoluble particulate solid are mixed in bulk or as a suspension in a solvent or suspending agent, the anti-discoloration stabilizers to be used according to the invention, if in dissolved or liquid form and optional others Stabilizers can optionally be mixed in solution or in liquid form. Preferably, the stabilizers are blended into the superabsorber as a powder or suspension because of the easier homogeneous distribution. In this case, a physical mixture which can not be separated easily by mechanical means is not necessarily produced. The additives may well enter into a firmer connection with the superabsorber, for example as a comparatively firmly adhering surface layer or as particles firmly adhering to the surface of the superabsorber particles. The interference of the additives in the known superabsorber can certainly also be understood and referred to as a "coating".

If a solution or suspension is used for the coating, a solvent or suspending agent is used as the solvent or suspending agent, which is chemically compatible with both the superabsorbent and the additive, that is to say that no undesired chemical reactions occur therewith. Typically, water or an organic solvent is used, for example an alcohol or polyol, or mixtures thereof. Examples of suitable solvents or suspending agents are water, isopropanol / water, 1,3-propanediol / water and propylene glycol. col / water, wherein the mixture mass ratio is preferably from 20:80 to 40:60. If a suspension agent is used for the stabilizers to be used according to the invention or the inorganic particulate solid, water is preferred. A surfactant may be added to the solution or suspension.

Stabilizers and other additives, unless added to the monomer mixture or to the polymerizing gel, are generally mixed with the superabsorbent in exactly the same way as the surface postcrosslinker-containing solution or suspension applied to the superabsorbent, such as described below. The additive can be applied to a (not) postcrosslinked superabsorber (a "base polymer" or "base polymer") as part of the solution applied to the surface postcrosslinking or one of its components, ie added to the solution of the surface postcrosslinker or one of its components. The superabsorber coated with surface postcrosslinking agents and additives then passes through the further process steps required for surface postcrosslinking, for example a thermally induced reaction of the surface postcrosslinking agent with the superabsorber. This process is comparatively simple and economical.

If the highest stability against discoloration is essential, stabilizers and additives are preferably applied after the surface postcrosslinking in a separate process step. If stabilizers and additives are applied as a solution or suspension, the application is carried out on the already surface-postcrosslinked superabsorber in the same way as the application of the surface postcrosslinker to the base polymer. Most, but not necessarily, is then heated as well as in the surface postcrosslinking to rewet the superabsorber. However, the temperature set in this drying is then generally at most 1 10 ° C, preferably at most 100 ° C, and most preferably at most 90 ° C to avoid undesirable reactions of the additive. The temperature is adjusted so that, in view of the residence time in the drying unit, the desired water content of the superabsorber is achieved. It is also possible and convenient to add the additive individually or together with other customary auxiliaries, for example dust binders, anti-caking agents or water for rewetting the superabsorber, as described below for these aids, for example in a cooler connected downstream of the surface postcrosslinking. The temperature of the polymer particles in this case is between 0 ° C and 190 ° C, preferably less than 160 ° C, more preferably less than 130 ° C, even more preferably less than 100 ° C, and most preferably less than 70 ° C , The polymer particles are optionally rapidly cooled to temperatures below a possible decomposition temperature of the additive after coating. Optionally, any known coatings, such as film-forming polymers, thermoplastic polymers, dendrimers, polycationic polymers (such as polyvinylamine, polyethylenimine or polyallylamine), or all of them, may be applied to the surface of the superabsorber particles, whether postcrosslinked or postcrosslinked, in the manufacturing process in any process step as required the water-soluble mono- or polyvalent metal salts known to the person skilled in the art, such as, for example, aluminum sulfate, sodium, potassium, zirconium or iron salts, are additionally applied. Examples of useful alkali metal salts are sodium and potassium sulfate, sodium and potassium lactates, citrates, sorbates. As a result, additional effects, for example a reduced tendency for the end product or the intermediate product to become clogged in the respective process step of the production process, improved processing properties or a further increased liquid conductivity (SFC), can be achieved. If additives are used and sprayed on in the form of dispersions, they are preferably used as aqueous dispersions, and it is preferable to additionally apply a dedusting agent for fixing the additive to the surface of the SAP. The dedusting agent is then added either directly to the dispersion of the inorganic powder additive, optionally it may also be added as a separate solution before, during, or after the inorganic powdery additive has been applied by spraying. Most preferred is the simultaneous spraying of postcrosslinking agent, dedusting agent and powdery inorganic additive in the postcrosslinking. In a further preferred variant of the method, however, the dedusting agent is added separately in the cooler, for example by spraying from above, below or from the side. Particularly suitable dedusting agents, which can also serve to fix powdery inorganic additives on the surface of the water-absorbing polymer particles, are polyethylene glycols having a molecular weight of 400 to 20,000 g / mol, polyglycerol, 3 to 100-fold ethoxylated polyols, such as trimethylolpropane, glycerol, sorbitol and neopentyl glycol. Particularly suitable are 7 to 20 times ethoxylated glycerol or trimethylolpropane, such as, for example, polyol TP ^70® (Perstorp, SE). The latter have the particular advantage that they only insignificantly reduce the surface tension of an aqueous extract of the water-absorbing polymer particles.

It is also possible to adjust the superabsorber according to the invention by adding water to a desired water content.

All coatings, solids, additives and auxiliaries can each be added in separate process steps, but in most cases the most convenient method is to add them, if they are not added during the displacement of the base polymer with surface postcrosslinking agent, to the superabsorber in the cooler, for example by spraying Solution or addition in finely divided solid or in liquid form. The superabsorbents according to the invention generally have a centrifuge retention capacity (CRC, measuring method see below) of at least 5 g / g, preferably of at least 10 g / g and in a particularly preferred form of at least 20 g / g. Usually it is not above 40 g / g.

The superabsorbers according to the invention, if they are surface-postcrosslinked, typically have an absorption under pressure (AUL0.7 psi, measuring method see below) of at least 18 g / g, preferably at least 20 g / g, preferably at least 22 g / g and usually not more than 30 g / g.

The superabsorbent according to the invention further typically have a saline flow conductivity (SFC measurement method s. Below) of at least 10x10 ^"7 cm ³ sec / g, preferably at least ^{30x10" 7} cm ³ sec / g, preferably at least 40x10 ^"7 cm ³ s / g and übli - not over 1000x10 ^"7 cm ³ s / g.

The L value of the superabsorber (CIE color number) in the non-stored state is typically at least 75, preferably at least 80, particularly preferably at least 85 and at most 100.

The a-value of the superabsorbent (CIE color number) in the non-stored state is typically from -2.5 to +2.5, preferably from -2.0 to +2.0, more preferably from -1.5 to +1 ; 5. The b-value of the superabsorbent (CIE color number) in the non-stored state is typically from 0 to 12, preferably from 2 to 1.

After the relatively stressful aging test described below, the superabsorber according to the invention, after measurement for the L and a values, has only slightly worse results compared to the non-stored state, in particular b values of preferably not more than 13, particularly preferably not more than 12, up. A b-value above 12 is critical in feminine hygiene articles and ultrathin diapers; a b-value of more than 15 is already critical in conventional diapers because this discoloration can be perceived by the consumer in use.

A further subject of the present invention are hygiene articles containing superabsorbents according to the invention, preferably ultrathin diapers, containing an absorbent layer consisting of 50 to 100 wt .-%, preferably 60 to 100 wt .-%, preferably 70 to 100 wt .-%, especially preferably from 80 to 100% by weight, very particularly preferably from 90 to 100% by weight, of superabsorbents according to the invention, wherein the coating of the absorbent layer is of course not taken into account. The superabsorbents according to the invention are also very particularly advantageous for the production of laminates and composite structures, as described, for example, in US 2003/0181115 and US 2004/0019342. In addition to the hot melt adhesives described in both documents for the production of such new absorbent structures, and more particularly the fibers of hot melt adhesives described in US 2003/0181115, to which the superabsorbent particles are bound, the superabsorbents of the invention are also suitable for the preparation of completely analogous Structures using UV-crosslinkable hotmelt adhesives which are sold, for example, as AC-Resin® (BASF SE, Germany). These UV-crosslinkable hot-melt adhesives have the advantage of being processable at as low as 120 to 140 ° C, so they are better compatible with many thermoplastic substrates. Another significant advantage is that UV-crosslinkable hot melt adhesives are toxicologically very harmless and also cause no exhalations in the toiletries. A very significant advantage, in connection with the superabsorbents according to the invention, is that the property of the UV-crosslinkable hotmelt adhesives does not tend to yellow during processing and crosslinking. This is particularly advantageous if ultrathin or partially transparent hygiene articles are to be produced. The combination of the superabsorbents according to the invention with UV-crosslinkable hotmelt adhesives is therefore particularly advantageous. Suitable UV-crosslinkable hot-melt adhesives are described, for example, in EP 0 377 199 A2, EP 0 445 641 A1, US Pat. No. 5,026,806, EP 0 655 465 A1 and EP 0 377 191 A2.

The superabsorbent according to the invention can also be used in other fields of technology in which liquids, in particular water or aqueous solutions, are absorbed. These areas are for example storage, packaging, transport (as components of packaging material for water or moisture sensitive articles, such as flower transport, as well as protection against mechanical effects); Animal hygiene (in cat litter); Food packaging (transport of fish, fresh meat, absorption of water, blood in fresh fish or meat packaging); Medicine (wound plaster, water-absorbing material for burn dressings or for other weeping wounds), cosmetics (carrier material for pharmaceutical chemicals and medicaments, rheumatism plaster, ultrasound gel, cooling gel, cosmetic thickener, sunscreen); Thickener for oil / water or water / oil emulsions; Textiles (moisture regulation in textiles, shoe inserts, for evaporative cooling, for example in protective clothing, gloves, headbands); chemical-technical applications (as a catalyst for organic reactions, for the immobilization of large functional molecules such as enzymes, as adhesives in agglomerations, heat storage, filtration aids, hydrophilic component in polymer laminates, dispersants, condenser); as an aid in powder injection molding, in construction and construction (installation, in clay-based plasters, as a vibration-inhibiting medium, aids in tunnel excavations in water-rich underground, cable sheathing); Water treatment, waste treatment, water separation (deicing, reusable Sandbags); Cleaning; Agribusiness (irrigation, retention of meltwater and dew precipitation, addition of compost, protection of forests against fungal / insect attack, delayed release of active substances into plants); for fire fighting or fire protection; Coextrusion agents in thermoplastic polymers (eg for the hydrophilization of multilayer films); Production of films and thermoplastic moldings capable of absorbing water (eg rain and condensation water-storing films for agriculture; superabsorbent-containing films for keeping fruit and vegetables fresh and packed in wet films; superabsorber-polystyrene coextrudates, for example for food packaging such as meat, fish, poultry, fruits and vegetables); or as a carrier substance in active ingredient formulations (pharmaceuticals, crop protection).

The liquid absorption articles according to the invention differ from those known in that they contain the superabsorber according to the invention.

A process has also been found for the preparation of articles for the absorption of liquid, in particular hygiene articles, which is characterized in that at least one superabsorber according to the invention is used in the production of the article in question. Incidentally, methods for producing such articles using superabsorbents are known.

test methods

The superabsorbent is tested using the test methods described below.

The "WSP" standard test methods described below are described in: "Standard Test Methods for the Nonwovens Industry", 2005 edition, co-edited by the Worldwide Strategy Partners EDANA (European Disposables and Nonwovens Association, Avenue Eugene Plasky). 157, 1030 Brussels, Belgium, www.edana.org) and INDA (Association of the Nonwoven

Fabrics Industry, 1 100 Crescent Green, Suite 1 15, Cary, North Carolina 27518, U.S.A., www.inda.org). This publication is available from both EDANA and INDA. All measurements described below should be performed at an ambient temperature of 23 ± 2 ° C and a relative humidity of 50 ± 10% unless otherwise specified. The superabsorbent particles are thoroughly mixed before measurement, unless stated otherwise.

Centrifuge Retention Capacity (CRC) The centrifuge retention capacity of the superabsorbent is determined according to the standard test method no. WSP 241.5-05 "Centrifuge retention capacity".

Absorption under pressure (AUL0.3psi, "Absorbency Under Load of 0.3 psi")

The absorption under a pressure of 2068 Pa (0.3 psi) of the superabsorbent is determined according to the standard test method no. WSP 242.2-05 "Absorption under pressure". Absorption under pressure (AUL0.7psi, "Absorbency Under Load of 0.7 psi)

The absorption under a pressure of 4826 Pa (0.7 psi) of the superabsorbent is determined analogously to the standard test method no. WSP 242.2-05 "absorption under pressure", but with a weight of 49 g / cm ² (leads to a pressure of 0.7 psi) instead of a weight of 21 g / cm ² (leading to a pressure of 0.3 psi) is used.

Fluid Transfer (SFC, "Saline Flow Conductivity")

The fluid transfer of a swollen gel layer formed by the superabsorber by liquid absorption is determined under pressure load of 0.3 psi (2068 Pa), as described in EP 0 640 330 A1, as gel layer permeability of a swollen gel layer of superabsorbent particles, wherein the in aforementioned patent application Page 19 and modified in Figure 8 is modified so that the glass frit (40) is no longer used, the punch (39) consists of ies more plastic material as the cylinder (37) and now evenly distributed over the entire support surface 21 of equal size Contains holes. The procedure and evaluation of the measurement remains unchanged compared to EP 0 640 330 A1. The flow is automatically detected. Fluid transfer (SFC) is calculated as follows:

SFC [cm ³ s / g] = (F g (t = 0) x L 0) / (dxAx WP), where F g (t = 0) is the NaCI solution flow in g / s calculated from a linear regression analysis of data Fg (t) of flow determinations by extrapolation to t = 0, L0 is the thickness of the gel layer in cm, d is the density of the NaCl solution in g / cm ^3, A is the area of the gel layer in cm ^2, and WP the hydrostatic pressure over the Gel layer in dyn / cm ² represents.

Permeability (FSGBP, Free Swell Gel Bed Permeability) The permeability is determined as described in US 2005/0 256 757 A1 in paragraphs [0061] to [0075].

Moisture content of the hydrogel (residual moisture, water content)

The water content of the water-absorbing polymer particles is determined according to the standard test method no. WSP 230.2-05 "Moisture content".

Mean particle size

The mean particle size of the product fraction is determined according to the standard test method no. WSP 220.2-05 "Particle size distribution".

CIE color number (L, a, b)

The color measurement is carried out according to the CIELAB method (Hunterlab, Volume 8, Volume 1996, No. 7, pages 1 to 4) with a colorimeter, model "LabScan XE S / N LX17309" (HunterLab, Reston, USA) Let L describe the colors L, a and b of a three-dimensional system, where L is the brightness, where L = 0 means black and L = 100. The values for a and b indicate the position of the color on the red / green color axes or yellow / blue, where + a stands for red, -a for green, + b for yellow and -b for blue According to the formula HC60 = L-3b, the HC60 value is calculated DIN 5033-6.

aging test

Measurement 1 (initial color): A 9 cm inner diameter plastic dish is filled with superabsorbent particles and then smoothed over the edge with a knife and the CIE color numbers and HC60 value are determined.

Measurement 2 (after aging): A 9 cm inner diameter plastic dish is filled with superabsorbent particles and then smoothed over the edge with a knife. The dish is then placed open in a controlled at 60 ° C cabinet with a constant relative humidity of 86%. The peel is taken out after 21 days. After cooling to room temperature, the CIE color numbers are determined.

Examples

General Procedure I: dry mixtures The components to be mixed are placed in a polyethylene sample bottle (500 ml capacity) and intimately mixed with a tumble mixer (type T2C, Willy A. Bachofen AG Maschinenfabrik, Basel, Switzerland) for 15 minutes.

General Procedure II: Wet Mixture

The superabsorbent is in a Pflugschar ^® mixer (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener Straße 7 - 9, 33102 Paderborn, Germany, type M5) at room temperature and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with respectively coated amount of the respective solution. After spraying, mixing is continued for 15 minutes at a shaft speed of 80 revolutions per minute, the product is dried in a vacuum drying oven at 80 ° C. and 250 mbar pressure for 60 minutes and freed from lumps by means of an 850 μm sieve.

As basis for the examples 1 to 15 of the commercially available superabsorbent Hysorb ^® B was 7055 (BASF SE, Ludwigshafen, Germany) was used. example 1

100 g HySorb ^® B 7055 was mixed with 0.050 g of 2,6-di-tert-butyl-4-methyl-phenol according to general procedure I. Example 2

100 g HySorb ^® B 7055 were [monoethyl (3,5-di-hydroxibenzyl tert-butyl-4) phosphonate] mixed with 0.060 g of calcium bis according to general procedure I. Example 3

100 g HySorb ^® B 7055 was mixed with 0.075 g of 3,5-di-tert-butyl-4-hydroxiphenylpropion- acid according to general procedure I mixed. Example 4

100 g HySorb ^® B 7055 was mixed with 0.100 g of 4,4-thio-bis (6-tert-butyl-meta-cresol) according to general procedure I.

Example 5 100 g HySorb ^® B 7055 were mixed with 0,040 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) according to general procedure I mixed.

Example 6

100 g HySorb ^® B 7055 were propionate with 0.130 g octadecyl-3- (3,5-di-tert-butyl-4-hydroxybenzophenone phenyl)) according to the general procedure I mixed.

Example 7

100 g HySorb ^® B 7055 were 4,6-bis mixed with 0.050 g (dodecylthiomethyl) -ortho-cresol according to the general procedure I.

Example 8

100 g HySorb ^® B 7055 was mixed with 0.070 g of 3,3 ', 3', 5,5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl ) tri-para-cresol according to general procedure I.

Example 9

100 g HySorb ^® B 7055 were, 3-diylbis ((3,5-di-tert-butyl-4-hydroxiphenylpropionamid) 3-) mixed with 0.050 g N, N-hexane-1 according to the general procedure I.

Example 10

100 g HySorb ^® B 7055 was mixed with 0.050 g of tris (2,4-di-tert-butylphenyl) phosphite according to general procedure I mixed.

Example 1 1

100 g HySorb ^® B 7055 were 3,9-bis (octa-decyloxi) -2,4,8,10-tetraoxa-3,9-diphosphaspiro undecane mixed with 0.060 g [5.5] according to general procedure I.

Example 12

100 g HySorb ^® B 7055 was mixed with 0.040 g of bis (2,4-di-tert-butylphenol) pentaerythritol diphosphite according to the general procedure I mixed.

Example 13 HySorb ^® 7055 B was prepared according to general procedure II with 1, 5 wt .-%, based on the amount of the superabsorbent, of a 4.0 wt .-% solution of calcium bis [monoethyl (3,5-di-tert .-Butyl-4-hydroxibenzyl) phosphonate] in methanol. Example 14

HySorb ^® 7055 B was prepared according to general procedure II with 2.0 wt .-%, based on the amount of the superabsorbent, of a 2.5 wt .-% solution of tris (2, 4-d i-tert- butylphenyl) phosphite in iso-propanol.

Example 15

HySorb ^® B 7055 was obtained with 0.5 wt .-%, according to the general procedure II bis-3- (5-tert on the amount of the superabsorbent, of a 40 wt .-% aqueous dispersion of ethylene lenbis (oxyethylene) .-Butyl-4-hydroxy-m-tolyl) -propionate). Notwithstanding the general rule II, the product was not dried, but sieved directly after mixing.

The coated superabsorbers thus prepared were subjected to the aging test. The results are summarized in Table 1. The examples show that the superabsorbers according to the invention are much lighter and less discolored after aging.

Table 1

*) Quantity in each case based on superabsorbent; **) initial color L = 93.4; a = 3.7; b = 4.8; HC60 = 79.1

Example V16 (comparison)

326.7 g of 50% strength by weight sodium hydroxide solution and 675 g of frozen, deionized water were placed in a 2 l stainless steel beaker. With stirring, 392.0 g of acrylic acid were added, adjusting the rate of addition so that the temperature did not exceed 35 ° C. The mixture was then cooled with stirring by means of a cooling bath. (Ludwigshafen, Germany Laromer ^® PO 9044V, BASF SE), 0.041 g of 2-hydroxy-2-methyl-1 -phenylpropan- 1 when the temperature of the mixture had dropped to 20 ° C, 08 g triacrylate were 1 triple ethoxylated glycerol -one (DAROCUR ^® 1173, Ciba Specialty Chemicals Inc., Basel, Switzerland) and 0.014 g of 2,2-dimethoxy-1, 2-diphenylethane-1-one (IRGACURE® 651, Ciba Specialty Chemicals Inc., Basel, Switzerland ) was added. It was further cooled, and upon reaching

15 ° C, the mixture was freed by passing nitrogen through a glass frit of oxygen. When reaching 0 ° C, 0.51 g of sodium persulfate (dissolved in 5 ml of water) and 0.06 g of hydrogen peroxide (dissolved in 6 ml of water) were added and the monomer solution was transferred to a glass dish. The glass dish was dimensioned such that a layer thickness of the monomer solution of 5 cm was established. Subsequently, 0.047 g of mixture were acid from the sodium salt of 2-hydroxy-2-sulfinatoessig-, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite (Brüggolit ^® FF6, L. Brüggemann KG, Salzstraße 131, 74076 Heilbronn, Germany), dissolved in 5 ml of water, was added and the monomer solution was stirred briefly using a glass rod. The glass dish with the monomer solution was placed under a UV lamp (UV intensity = 25 mW / cm ² ), the polymerization started. To

For 16 minutes, the gel obtained was wound three times with the aid of a commercially available meat grinder with a 6 mm perforated disc and in the laboratory drying cupboard at 160 ° C.

Dried for an hour. The product was then ground and the sieve fraction was recovered from 150-850 μηη.

This base polymer was for surface postcrosslinking in a ploughshare ^® - mixer with heating jacket (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener- 7 - 9, 33102 Paderborn, Germany; Type M5.) At room temperature and a shaft speed of 450 revolutions per minute by means of a two-substance -Sprühdüse with a mixture of 0.10 wt .-% ethylene glycol diglycidyl ether (Denacol EX-810 ^® from Nagase ChemteX Corporation, Osaka, Japan) by weight, 1 50 .-% 1, 2-propanediol, 2.8 wt .-% Water and 0.4 wt .-% aqueous aluminum sulfate solution (26.8 wt .-%), each based on the base polymer, coated.

After spraying, the product temperature was raised to 150 ° C and the reaction mixture was maintained at that temperature for 60 minutes at a shaft speed of 80 revolutions per minute. The resulting product was allowed to cool back to room temperature and sieved. The surface-postcrosslinked superabsorber was obtained as a sieve fraction with particle sizes between 150 μm and 850 μm. Examples 16 to 20

150 g of the superabsorber of Example V16 were according to general procedure I, 0.15 g of a hydrophobic precipitated silica (Sipernat ^® D-17, Evonik Degussa GmbH, Frankfurt am Main, Germany) and the amounts of calcium bis [shown in the following Table 2 monoethyl (3,5-di-tert-butyl-4-hydroxypentyl) phosphonate].

The coated superabsorbers produced in this way were subjected to the aging test. The results are summarized in Table 2. The examples show that even small amounts of the stabilizer stabilize the superabsorber according to the invention against discoloration on aging.

Table 2

 *) Quantity in each case based on superabsorbent;

^** ) initial color L = 88.7; a = -0.4; b = 9.0; HC60 = 61, 7 Examples 21 to 25

150 g of the superabsorber of Example V16 were according to general procedure I, 0.15 g of a hydrophobic precipitated silica (Sipernat ^® D-17, Evonik Degussa GmbH, Frankfurt am Main, Germany) and the amounts indicated in Table 3 below tris (2,4-di-tert-butylphenyl) phosphite.

The coated superabsorbers thus prepared were subjected to the aging test. The results are summarized in Table 3. The examples show that even small amounts of the stabilizer stabilize the superabsorber according to the invention against discoloration on aging. Table 3

 *) Quantity in each case based on superabsorbent;

 **) initial color L = 88.7; a = -0.4; b = 9.0; HC60

Example 26

Example V16 was repeated except that the monomer solution was additionally added with 0.59 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxibenzyl) phosphonate] prior to further cooling to 15 ° C.

Example 27

Example V16 was repeated except that 0.59 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] was added to the gel in the wake.

The superabsorbents prepared in this way were subjected to the aging test. The results are summarized in Table 4. The examples show that even small amounts of the stabilizer stabilize the superabsorber according to the invention against discoloration on aging.

Table 4

 *) Amount in each case based on acrylic acid;

**) initial color L = 88.7; a = -0.4; b = 9.0; HC60 = 61, 7 Example V 28 (cf.

14.3 kg of sodium acrylate aqueous solution (37.5 wt .-% solution in deionized water), 1, 4 kg of acrylic acid and 350 g of deionized water with 18.5 g Triacry- lat threefold ethoxylated glycerol (Laromer PO 9044V ^® BASF SE, Ludwigshafen, Germany). This solution was placed in a heated nitrogen sparge drop tower (180 ° C, 12 m high, 2 m diameter, 0.1 m / s gas velocity, 40 mm diameter dropper, 2 mm internal height, and 60 drilled holes in 200 μηη of diameter) at a rate of 32 kg / h, their temperature was 25 ° C. Shortly before the dropletizer, the monomer solution was mixed via a static mixer with two initiator solutions. As initiator 1, a 3 wt .-% solution of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in deionized water, as initiator 2, a 6.1 wt. % solution of sodium peroxodisulfate in deionized water. The metering rate of the initiator solution 1 was 1.462 kg / h, the metering rate of the solution 2 was 0.629 kg / h. The resulting polymer particles were screened to separate any agglomerates formed. The sieve fraction of 150 to 850 μηη was recovered as a product. Example 28

100 g of the superabsorbent of Example V28 were mixed with 0.10 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) according to general procedure I.

Example 29

100 g of the superabsorbent of Example V28 were mixed with 0.10 g of tris (2,4-di-tert-butylphenyl) phosphite according to general procedure I.

Example 30

100 g of the superabsorbent of Example V28 were mixed with 0.05 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and 0.05 g of tris (2,4-di tert-butylphenyl) phosphite according to general procedure I.

The superabsorbents prepared in this way were subjected to the aging test. The results are summarized in Table 5. The examples show that the superabsorbers according to the invention are much lighter and less discolored after aging. But they also show that mixtures can work synergistically. Example V31 (comparison)

14.3 kg of sodium acrylate aqueous solution (37.5 wt .-% solution in deionized water), 1, 4 kg of acrylic acid and 350 g of deionized water were mixed with 6.6 g triacrylate threefold ethoxylated glycerol (Laromer PO 9044V ^®, BASF SE, Ludwigshafen,

Germany) mixed. This solution was placed in a heated nitrogen sparge drop tower (180 ° C, 12 m high, 2 m diameter, 0.1 m / s gas velocity, 40 mm diameter dropper, 2 mm internal height, and 60 drilled holes in 200 μηη of diameter) at a rate of 32 kg / h, their temperature was 25 ° C. Shortly before the dropletizer, the monomer solution was mixed via a static mixer with three initiator solutions. As initiator 1, a 3 wt .-% solution of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in deionized water, as initiator 2, a 6.1 wt. -% solution of sodium peroxodisulfate in deionized water and as initiator 3, a 3 wt .-% solution of ascorbic acid in deionized water was used. The metering rate of the initiator solution 1 was 0.548 kg / h, the metering rate of the solution 2 was 0.449 kg / h and the metering rate of the solution 3 was 0.183 kg / h. The resulting polymer particles were screened to separate any agglomerates formed. The sieve fraction of 150 to 850 μηη was recovered as a product.

Example V32 (comparison)

14.3 kg of sodium acrylate aqueous solution (37.5 wt .-% solution in deionized water), 1, 4 kg of acrylic acid and 350 g of deionized water were mixed with 6.6 g triacrylate threefold ethoxylated glycerol (Laromer PO 9044V ^®, BASF SE, Ludwigshafen, Germany). This solution was placed in a heated, nitrogen-filled drip tower (180 ° C, 12 m high, 2 m diameter, gas velocity 0.1 m / s cocurrent, 40 mm diameter dropper, 2 mm internal height, and a 60 ° dropper plate 200 μηη diameter holes) at a rate of 32 kg / h, their temperature was thereby 25 ° C. Shortly before the dropletizer, the monomer solution was mixed via a static mixer with three initiator solutions. As initiator 1, a 3 wt .-% solution of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in deionized water, as initiator 2, a 6.1 wt. -% solution of sodium peroxodisulfate in deionized water and as initiator 3 was a 3 wt .-% solution of a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoessig- acid and sodium bisulfite (Brüggolit ^® FF7, L. Brüggemann KG, salt Straße 131, 74076 Heilbronn, Germany) in deionized water. The metering rate of the initiator solution 1 was 0.548 kg / h, the metering rate of the solution 2 was 0.449 kg / h and the metering rate of the solution 3 was 0.183 kg / h. The obtained polymer particles were sieved to separate any formed agglomerates. The sieve fraction of 150 to 850 μηη was recovered as a product.

Example 31

100 g of the superabsorber of Example V31 were mixed with 0.10 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxypentyl) phosphonate] according to general procedure I. Example 32

100 g of the superabsorber of Example V32 were mixed with 0.10 g of diethyl (3,5-di-tert-butyl-4-hydroxibenzyl) phosphonate according to general procedure I. The superabsorbents prepared in this way were subjected to the aging test. The results are summarized in Table 6. The examples show that the superabsorbers according to the invention are much lighter and less discolored after aging.

Example V33 (comparison)

In a Pflugschar ^® paddle dryer with 5 l volume and heating / cooling jacket (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener-Straße 7 - 9, 33102 Paderborn, Germany, type VT 5R-MK) were 478 g of water, 244.3 g acrylic acid, 1924.9 g of a 37.3 wt .-% sodium acrylate solution (to 100 mol% neutralized acrylic acid, ie without free acrylic acid or free sodium salt), 16.0 g of calcium carbonate and 2.52 g triacrylate tri ethoxylated glycerol ( Laromer PO 9044V ^®, BASF SE; Ludwigshafen, Germany), and 20 minutes presented inertization Siert by bubbling nitrogen. The shaft of the reactor was rotated continuously at 96 revolutions per minute. The reaction mixture was cooled from the outside so that the subsequent addition of initiator took place at about 20 ° C. Finally, with stirring 2.199 g of sodium persulfate (dissolved in 12.12 g of water), 0.046 g of ascorbic acid (dissolved in 9.12 g of water) and 0.127 g of 30 wt .-% aqueous hydrogen peroxide solution (diluted with 1 , 15 g of water) are added rapidly in succession. The reaction started quickly and when reaching an internal temperature of 30 ° C, the jacket was heated with 80 ° C hot heat transfer medium to perform the reaction as adiabatic as possible to an end. After reaching the maximum temperature was again cooled (cooling liquid at -12 ° C), so the resulting gel was cooled to below 50 ° C and then discharged. The gel was then dried in a laboratory oven at 160 ° C for one hour. The product was then ground and the sieve fraction was recovered from 150-700 μηη. This base polymer was for surface postcrosslinking in a ploughshare ^® - mixer with heating jacket (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener- 7 - 9, 33102 Paderborn, Germany; Type M5.) At room temperature and a shaft speed of 450 revolutions per minute by means of a two-substance Spray nozzle with a mixture of 0.125 wt .-% N- (2-hydroxyethyl) -2-oxazolidinone, 1, 5 wt .-% water, 1, 5 wt.% 1, 3-propanediol, 0.003 wt .-% sorbitan monococoate (" ^Span® 20") and 2.8% by weight of a 25% by weight aqueous aluminum lactate solution, based in each case on the base polymer After spraying, the product temperature was raised to 175 ° C. and the reaction mixture 80 The resulting product was allowed to cool back to room temperature and sieved The surface-postcrosslinked superabsorber was used as a sieve fraction with particle sizes between 150 μ η and μηη won the 710th Example 33

100 g of the superabsorbent of Example V26 were mixed with 0.050 g of 2,2'-ethylidenebis [4,6-bis (1,1-dimethylethyl) phenol] according to general procedure I. Example 34

Example V33 was repeated, but in the case of surface postcrosslinking, the base polymer was additionally coated with 0.2% by weight of tris- (2,4-di-tert-butylphenyl) phosphite, based on the base polymer.

Example 35

Example V33 (comparison) was repeated, but in the polymerization after reaching an internal temperature of 60 ° C of the reaction mixture in Pflugschar ^® paddle dryer still 1, 2 g pentaerythritol tetrakis (3- (3,5-di-tert. -butyl-4-hydroxyphenyl) propionate).

The superabsorbents prepared in this way were subjected to the aging test. The results are summarized in Table 7. The examples show that the superabsorbents according to the invention are much lighter and less discolored after aging, without the absorption properties being impaired. Table 5

^* ) Quantity in each case based on superabsorbent; ^** ) initial color L = 93.4; a = 0.6; b = 2.1; HC60 = 87.1

Table 6

^* ) Quantity in each case based on superabsorbent; ^** ) initial color L = 99.3; a = 0.2; b = -1.5; HC60 = 103.8;

) initial color L = 96.2; a = 0.5; b = -1.5; HC60

Table 7

Claims

claims 1 . Superabsorber containing at least one discoloration stabilizer selected from phenols, phosphonic acid (HP (0) (OH) 2), phosphorous acid (H3PO3), and the salts and esters of these acids. 2. Superabsorber according to claim 1, characterized in that it contains calcium, strontium or barium. 3. Superabsorber according to claim 1 or 2, characterized in that it further contains at least one selected from derivatives of sulfinic acid compound and / or at least one inorganic water-insoluble particulate solid. 4. Superabsorber according to claims 1 to 3, characterized in that it comprises a crosslinked, partially neutralized polymer of at least one ethylenically unsaturated, at least one acid group-carrying monomer. 5. Superabsorber according to one of claims 1 to 4, characterized in that the monomer is acrylic acid. 6. Superabsorber according to one of claims 1 to 5, characterized in that it is surface postcrosslinked. 7. Superabsorber according to one of claims 1 to 5, characterized in that the stabilizer is added to it in predominantly undissolved form. 8. A process for preparing a superabsorbent as defined in claims 1 to 7, wherein the superabsorber during or after its preparation a stabilizer against discoloration consisting of phenols, phosphinic acid (H3PO2), Phosphonic acid (HP (0) (OH) 2), phosphorous acid (H3PO3), and the salts and esters of these acids is added. 9. The method according to claim 8, characterized in that one adds the stabilizer in predominantly undissolved form. 10. An article for the absorption of liquids, comprising one of the defined in claims 1 to 7 superabsorbent. 1 1. Process for the preparation of articles for the absorption of liquid, characterized in that during production one of the superabsorbers defined in claims 1 to 7 is used.