DE19926431A1 - Absorbent mixture - Google Patents

Abstract

The invention relates to an absorbent mixture that contains (a) an organic iodine compound and (b) a hydrogel-forming polymer, the share of the iodine compound being 0.001 to 5 wt.- % of the hydrogel-forming polymer. The invention also relates to the use of said mixture in incontinence products and to incontinence articles containing said mixture.

Description

The present invention relates to an absorbent mixture containing

• a) an organic iodine compound and
• b) a hydrogel-forming polymer,

wherein the proportion of the iodine compound 0.001 to 5 wt .-% of the hydro gel-forming polymer and the use of these Mix in incontinence articles for adults and babies as well incontinence articles containing them. Furthermore, it affects the Use of organic iodine compounds in incontinence areas keln.

Diaper rash is a common form of skin irritation Inflammation or inflammation of parts of the body that normally occur covered by wearing diaper. Especially poses Diaper rash is a serious problem in adult incontinence It is generally accepted that the Win del-dermatitis is a contact dermatitis caused by long-term contact of the skin with urine and / or faeces stands. To date, the exact components are in urine and faeces lien, which is responsible for the appearance of diaper rash are not fully known in their entirety. It However, it can be assumed that ammonia, bacteria, Mushrooms, moisture and skin pH play a crucial role play in the development of diaper dermatitis. In addition to the skin The long-lasting contact leads to irritation or inflammation Skin with urine and feces also for the development of bad Odors, especially those of incontinence articles Adults are found to be extremely uncomfortable.

Many attempts have been made to address these two problems to solve.

On the one hand, attempts were made to cover the smell with fragrances cover as described in JP-A-0 605 1843 and the other bind by zeolites, as described in WO 95/26207. Such measures reduce the perception of uncomfortable Smells, but not the appearance of skin irritation and inflammation.  

Skin irritation occurs more often when the natural acidity protective skin is destroyed. This is done by increasing The pH value, for example, due to the decomposition of the urine by urease to ammonia.

EP-A 0 739 635 therefore teaches those containing sodium tetraborate Hydrogels that act as urease inhibitors.

There are also numerous attempts, by buffer substances or according to materials bearing acid groups at difference most diaper parts to achieve a skin-neutral pH. EP-A-0 316 518 teaches hydrogels which, when wetted with water have a pH of 5.2 to 5.5. Furthermore, ion exchange ends modified cellulose in EP-A-0 202 126 as a cover layer and described in EP A-0 202 127 as core material. All these approaches have in common that the emergence of the skin irritating components is not prevented, and the we creases with longer contact times.

EP-A-0 837 077, EP-A-0 839 841 and WO 92/06694 describe the use of quaternary ammonium salts such as cetyl pyridi nium chloride or didecyldimethylammonium carbonate as microbiocides Additives for the hydrogel. The disadvantage, however, is that this Connections themselves are not very skin-friendly and too cause allergic reactions.

The present invention therefore has an absorbent mixture as a task that, when used in articles for Ab sorption of body fluids does not follow the above has parts.

Accordingly, the above-mentioned absorbent mixtures, their Use in incontinence articles and incontinence articles holding the mixtures according to the invention found.

An absorbent mixture is to be understood as a mixture that contains a hydrogel-forming polymer as the main ingredient. The mixture according to the invention preferably consists of an orga African iodine compound, the hydrogel-forming polymer and given if necessary for hydrogel additives.

Organic iodine compounds (a) are compounds that contain iodine contain covalently or complex bound. Such connections split iodine relatively in contact with aqueous liquids slightly off.  

Organic iodine compounds that contain iodine bound in a complex are, for example, polyvinylpyrrolidone-iodine complex and starch Iodine complexes.

Covalent iodine compounds are particularly preferred 3-iodo-2-propynyl-N-butyl carbamate and 4-methylphenyldiiodomethyl sulfone.

The proportion of the organic iodine compound based on the total weight of the absorbent mixture is 0.001 to 5% by weight, preferably 0.005 to 1% by weight, in particular 0.01 to 0.5% by weight.

Hydrogel-forming polymers (b) are crosslinked polymers with acid groups, mostly in the form of their salts, usually Alkali or ammonium salts are present. Such polymers swell gel on contact with aqueous liquids.

Polymers (b) obtained by crosslinking polymerization are preferred or copolymerization of monoethylenic acid groups unsaturated monomers or their salts can be obtained. Further it is possible to (co) polymerize these monomers without crosslinking agents and subsequently networked.

Monomers bearing such acid groups are, for example, mono-ethylenically unsaturated C ₃ -C ₂₅ -carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. Also suitable are monoethylenically unsaturated sulfonic or phosphonic acids, for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropylacrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxy propylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, vinylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, allylphosphonic acid, vinylphosphonic acid, allylphosphonic acid, allylphosphonic acid, vinylphosphonic acid, allylphosphonic acid, vinylphosphonic acid, allylphosphonic acid, vinylphosphonic acid, allylphosphonic acid and vinylphosphonic acid, allylphosphonylphosphonic acid, and vinylphosphonic acid, allylphosphonophosphonic acid, -2-methylpropanesulfonic acid. The monomers can be used alone or as a mixture with one another.

Monomers used with preference are acrylic acid, methacrylic acid. Vinylsulfonic acid, acrylamidopropanesulfonic acid or mixtures these acids, e.g. B. mixtures of acrylic acid and methacrylic acid, Mixtures of acrylic acid and acrylamidopropanesulfonic acid or Mixtures of acrylic acid and vinyl sulfonic acid.

To optimize properties, it may be useful to use additional monoethylenically unsaturated compounds which do not carry an acid group but are copolymerizable with the monomers bearing acid groups. These include, for example, the amides and nitriles of monoethylenically unsaturated carboxylic acids, e.g. B. acrylamide, methacrylamide and N-vinylformamide, N-Vinylaceta mid, N-methyl-N-vinylacetamide, acrylonitrile and methacrylonitrile. Other suitable compounds are, for example, vinyl esters of saturated C ₁ - to C ₄ -carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate, alkyl vinyl ethers with at least 2 C atoms in the alkyl group, such as, for. B. ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, for. B. esters of monohydric C ₁ - to C ₁₈ alcohols and acrylic acid, methacrylic acid or maleic acid, half esters of maleic acid, e.g. B. maleic acid monomethyl ester, N-vinyl lactams such as N-vinyl pyrrolidone or N-vinyl caprolactam, acrylic acid and methacrylic acid esters of alkoxylated monohydric, saturated alcohols, e.g. B. from Alko fetch with 10 to 25 carbon atoms that have been reacted with 2 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol, such as monoacrylic acid esters and monomethacrylic acid esters of polyethyleneglycol or polypropylene glycol, the molar masses (M _N ) of Polyalkylene glycols can be up to 2000, for example. Other suitable monomers are styrene and alkyl-substituted styrenes such as ethylstyrene or tert. Butyl styrene.

These monomers not bearing acid groups can also be used in Mixture with other monomers are used, for. B. Mixtures from vinyl acetate and 2-hydroxyethyl acrylate in any Relationship. These will not be monomers bearing acid groups the reaction mixture in amounts between 0 and 50% by weight, preferably less than 10 wt .-% added.

Crosslinked polymers bearing acid groups are preferred monoethylenically unsaturated monomers, which may be present or after the polymerization into their alkali or ammonium salts be transferred, and from 0-40 wt .-% based on their total Ge important monoethylenically unsaturated ones not bearing acid groups Monomers.

Crosslinked polymers (b) of monoethylenically unsaturated C ₃ -C ₁₂ carboxylic acids and / or their alkali metal or ammonium salts are preferred. In particular, crosslinked polyacrylic acids are preferred, the acid groups of which are 50-100% in the form of alkali or ammonium salts.

Compounds which have at least 2 have ethylenically unsaturated double bonds. examples for Compounds of this type are N, N'-methylene-bisacrylamide, poly ethylene glycol diacrylates and polyethylene glycol dimethacrylates, the each of polyethylene glycols with a molecular weight of 106 to 8500, preferably 400 to 2000, trimethylol  propane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexane diol diacrylate, hexanediol dimethacrylate, allyl methacrylate, Diacrylates and dimethacrylates from block copolymers Ethylene oxide and propylene oxide, two or three times with acrylic acid or methacrylic acid esterified polyhydric alcohols, such as Glycerin or pentaerythritol, triallylamine, tetraallylethylene diamine, divinylbenzene, diallyl phthalate, polyethylene glycol divinyl ethers of polyethylene glycols with a molecular weight of 126 to 4000, trimethylol propanediallyl ether, butanediol divinyl ether, Pentaerythritol triallyl ether and / or divinyl ethylene urea. Preferably, water-soluble crosslinking agents are used, e.g. B. N, N'- Methylene bisacrylamide, polyethylene glycol diacrylates and polyethylene lenglycol-dimethacrylate, which is derived from addition products of 2 up to 400 moles of ethylene oxide with 1 mole of a diol or polyol derive vinyl ethers from addition products from 2 to 400 mol Ethylene oxide with 1 mole of a diol or polyol, ethylene glycol diacrylate, ethylene glycol dimethacrylate or triacrylate and tri methacrylates of addition products of 6 to 20 moles of ethylene oxide to 1 mol of glycerol, pentaerythritol triallyl ether and / or divinyl urea.

Compounds which have min least a polymerizable ethylenically unsaturated group and contain at least one further functional group. The funk tional group of these crosslinkers must be able to use the functional groups, essentially the acid groups of the mono to react. Suitable functional groups are for example hydroxyl, amino, epoxy and aziridino groups. Can be used for. B. Hydroxyalkyl esters of the above ten monoethylenically unsaturated carboxylic acids, e.g. B. 2-hydroxy ethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl meth acrylate, dialkyldiallylammonium halides such as dimethyldiallylam monium chloride, diethyl diallyl ammonium chloride, allyl piperidinium bromide, N-vinylimidazoles such as e.g. B. N-vinylimidazole, 1-vinyl-2-methylimidazole and N-vinylimidazolines such as N-vinylimida zoline, 1-vinyl-2-methylimidazoline, 1-vinyl-2-ethylimidazoline or 1-vinyl-2-propylimidazoline, which is in the form of the free bases, in quaternized form or used as a salt in the polymerization can be set. Dialkylaminoalkyl are also suitable acrylates and dialkylaminoalkyl methacrylates, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate. The basic esters will preferably used in quaternized form or as a salt. Furthermore, e.g. B. Glycidyl (meth) acrylate can also be used.  

The crosslinkers in the reaction mixture are, for example, from 0.001 to 20 and preferably from 0.01 to 14 wt .-% present.

As usual, the polymerization is initiated by an initia gate triggered. Also initiation of the polymerization by Action of electron beams on the polymerizable, aqueous mixture is possible. The polymerization can, however even in the absence of initiators of the type mentioned above Exposure to high energy radiation in the presence of photo initiators are triggered. As polymerization initiators can all into radicals under the polymerization conditions disintegrating compounds are used, e.g. B. peroxides, hydro peroxides, hydrogen peroxide, persulfates, azo compounds and the so-called redox catalysts. The use of is preferred water-soluble initiators. In some cases it is an advantage liable to ver mixtures of different polymerization initiators turn, e.g. B. mixtures of hydrogen peroxide and sodium or Potassium peroxodisulfate. Mixtures of hydrogen peroxide and Sodium peroxodisulfate can be in any ratio be used. Suitable organic peroxides are examples wise acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-Bu tylperpivalat, tert-butyl perneohexanoate, tert-butyl perisobuty rat, tert-butyl per-2-ethylhexanoate, tert-butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, di- (2-ethyl hexyl) peroxidicarbonate, dicyclohexylperoxydicarbonate, Di- (4-tert-butylcyclohexyl) peroxidicarbonate, Dimyristil-peroxi dicarbonate, diacetyl peroxydicarbonate, allyl perester, cumyl peroxy neodecanoate, tert-butylper-3,5,5-tri-methylhexanoate, acetylcy clohexyl sulfonyl peroxide, dilauryl peroxide, dibenzoyl peroxide and tert-amyl perneodecanoate. Particularly suitable polymerisationini tiators are water-soluble azo starters, e.g. B. 2,2'-Azo bis- (2-amidinopropane) dihydrochloride, 2,2'-azobis- (N, N'-di methylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) iso butyronitrile, 2,2'-azobis [2- (2'-imidazolin-2-yl) propane] dihydro chloride and 4,4'-azobis (4-cyanovaleric acid). The mentioned Po polymerization initiators are used in conventional amounts, e.g. B. in amounts of 0.01 to 5, preferably 0.1 to 2.0 wt .-%, based on the monomers to be polymerized.

Redox catalysts are also suitable as initiators. The redox catalysts contain at least one of the above per-compounds as the oxidizing component and as reducing component, for example, ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide, metal salts , such as iron (II) ions or silver ions or sodium hydroxymethylsulfoxy lat. Ascorbic acid or sodium sulfite is preferably used as the reducing component of the redox catalyst. Based on the amount of monomers used in the polymerization, for example 3.10 ^-6 to 1 mol% of the reducing component of the redox catalyst system and 0.001 to 5.0 mol% of the oxidizing component of the redox catalyst are used.

If the polymerisation by exposure to high energy Triggers radiation, is usually used as an initiator called photoinitiators. This can be, for example so-called α-splitter, H-abstracting systems or azides act. Examples of such initiators are benzophenone deri vate such as Michlers ketone, phenanthrene derivatives, fluorene derivatives, Anthraquinone derivatives, thioxanone derivatives, coumarin derivatives, Benzoin ethers and their derivatives, azo compounds such as those above called radical formers, substituted hexaarylbisimidazoles or Acylphosphine oxides. Examples of azides are: 2- (N, N-dimethyl amino) ethyl 4-azidocinnamate, 2- (N, N-dimethylamino) ethyl 4-azi donaphthyl ketone, 2- (N, N-dimethylamino) ethyl 4-azidobenzoate, 5-Azido-1-naphthyl-2 '- (N, N-dimethylamino) ethyl sulfone, N- (4-sulfo nylazidophenyl) maleimide, N-acetyl-4-sulfonylazidoaniline, 4-sul fonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide, p-azide topzoic acid, 2,6-bis (p-azidobenzylidene) cyclohexanone and 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone. The photo If they are used, initiators are usually in Amounts of 0.01 to 5 wt .-%, based on the polymerize the monomers applied.

In the subsequent crosslinking, polymers are formed by the Polymerization of the above monoethylenically unsaturated Acids and optionally monoethylenically unsaturated Comono mers were produced and which have a molecular weight greater than 5000, preferably have greater than 50,000, reacted with compounds which at least two groups reactive towards acid groups point. This reaction can take place at room temperature or at he high temperatures up to 200 ° C.

The suitable functional groups have already been mentioned above, d. H. Hydroxyl, amino, epoxy, isocyanate, ester, amido and Aziridino groups. Examples of such crosslinkers are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycol, glycerin, polyglycerin, propylene glycol, poly propylene glycol, block copolymers of ethylene oxide and propylene oxide, sorbitan fatty acid ester, ethoxylated sorbitan fatty acid ester, trimethylolpropane, pentaerythritol, 1,3-butanediol, 1,4-butanediol, polyvinyl alcohol, sorbitol, polyglycidyl ether such as Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,  Glycerol diglycidyl ether, glycerol polyglycidyl ether, diglycerol po lyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglyci dyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglyci dyl ether and polypropylene glycol diglycidyl ether, polyaziridine ver bonds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) - propionate], 1,6-hexamethylene diethylene urea, diphenylmethane bis-4,4'-N, N'-diethylene urea, halo epoxy compounds such as Epichlorohydrin and α-methyl epifluorohydrin, polyisocyanates such as 2,4-tolylene diisocyanate and hexamethylene diisocyanate, alkylene carbonates such as 1,3-dioxolan-2-one and 4-methyl-1,3-dioxolan-2-one, furthermore bisoxazolines and oxazolidones, furthermore polyquaternary ones Amines such as condensation products of dimethylamine with epichlor hydrine, homo- and copolymers of diallyldimethylammonium chloride as well as homopolymers and copolymers of dimethylamino ethyl (meth) acrylate, optionally with, for example, methyl chloride are quaternized.

Other suitable crosslinkers for postcrosslinking are polyvalent ones Metal ions that are able to form ionic crosslinks form. Examples of such crosslinkers are magnesium, calcium, Barium and aluminum ions. These crosslinkers are, for example as hydroxides, carbonates or hydrogen carbonates of the aqueous po added lymerizable solution. Other suitable crosslinkers are multifunctional bases that are also able to to form ionic crosslinks, for example polyamines or their quaternized salts. Examples of polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pent amine, pentaethylene hexamine and polyethylene imines as well as polyvinyl amines with molecular weights of up to 4,000,000 each.

The crosslinkers are the polymers or acid group Salts in amounts of 0.5 to 25 wt .-% preferably from 1 to 15 wt .-%, based on the amount of polymer used puts.

The crosslinked polymers (b) are preferably used in neutralized form in the mixture according to the invention. However, the neutralization can also have been carried out only partially. The degree of neutralization is preferably 25 to 100%, in particular 50 to 100%. Possible neutralizing agents are:
Alkali metal bases or ammonia or amines. Sodium hydroxide solution or potassium hydroxide solution is preferably used. The neutralization can also be carried out with the aid of sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate or other carbonates or hydrogen carbonates or ammonia. In addition, prim., Sec. And tert. Amines can be used.

As a technical process for the manufacture of these products can all methods are used, which are usually used in the manufacture position of superabsorbers are used, as z. B. in Chapter 3 in "Modern Superabsorbent Polymer Technology", F. L. Buchholz and A. T. Graham, Wiley-VCH, 1998.

Polymerization in aqueous solution is preferred as so-called called gel polymerization. 10 to 70% by weight aqueous solutions of the monomers and, if appropriate, a suitable one Graft base in the presence of a free radical initiator polymerisation of the Trommsdorff-Norrish effect.

The polymerization reaction can take place in the temperature range between 0 and 150 ° C, preferably between 10 and 100 ° C, both at normal pressure as well as under increased or reduced pressure leads. As usual, the polymerization can also be carried out in a Protective gas atmosphere, preferably under nitrogen become.

By reheating the polymer gels for several hours at temperature range 50 to 130 ° C, preferably 70 to 100 ° C, the quali properties of the polymers can be improved.

Suitable polymers (b) are also graft (co) polymers of one or more hydrophilic monomers on a suitable graft basis, cross-linked, acid groups-bearing cellulose or Starch ether and ester, cross-linked carboxymethyl cellulose, or in aqueous liquids swellable natural products with acid groups, such as alginates and carrageenans.

Suitable graft bases can be of natural or synthetic origin. Examples are starch, cellulose or cellulose derivatives and other polysaccharides and oligosaccharides, poly vinyl alcohol, polyalkylene oxides, in particular polyethylene oxides and polypropylene oxides, polyamines, polyamides and hydrophilic polyesters. Suitable polyalkylene oxides have, for example, the formula

wherein
R ¹ and R ² independently of one another are hydrogen, alkyl, alkenyl or acrylic,
X is hydrogen or methyl and
n is an integer from 1 to 10,000.

R ¹ and R ^{2 are} preferably hydrogen, (C ₁ -C ₄ ) alkyl, (C ₂ -C ₆ ) alkenyl or phenyl.

Hydrogel-forming polymers (b) are preferred, the surfaces are cross-linked. The surface post-crosslinking can in itself known way with dried, ground and sieved Polymer particles happen.

For this purpose, compounds with the functional groups of the Polymers (b) can react with crosslinking, preferably in Form a water-based solution on the surface of the hydrogel Particles applied. The aqueous solution can be mixed with water Contain bare organic solvents. Suitable solvents are alcohols such as methanol, ethanol, i-propanol or acetone.

Suitable post-crosslinking agents are, for example

• - Di- or polyglycidyl compounds such as phosphonic acid diglyci dyl ether or ethylene glycol diglycidyl ether, bischlorohydrin ethers of polyalkylene glycols,
• - alkoxysilyl compounds,
• - Compounds containing polyaziridines, aziridine units based on polyethers or substituted hydrocarbons substances, for example bis-N-aziridinomethane,
• - Polyamines or polyamidoamines and their reaction products with epichlorohydrin,
• - Polyols such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, glycerol, methyltriglycol, polyethylene glycols with an average molecular weight M _W of 200-10000, di- and polyglycerol, pentaerythritol, sorbitol, the oxyethylates of these polyols and their Esters with carboxylic acids or carbonic acid such as ethylene carbonate or propylene carbonate,
• Carbonic acid derivatives such as urea, thiourea, guanidine, Dicyandiamide, 2-oxazolidinone and its derivatives, bisoxa zoline, polyoxazolines, di- and polyisocyanates,
• - Di- and poly-N-methylol compounds such as Methylenebis (N-methylol-methacrylamide) or melamine formaldehyde hyd resins,
• - Compounds with two or more blocked isocyanate groups such as trimethylhexamethylene diisocyanate with 2,2,3,6-tetramethyl-piperidinone-4.

If necessary, acidic catalysts such as p- Toluenesulfonic acid, phosphoric acid, boric acid or ammonium dihydro gene phosphate can be added.

Particularly suitable post-crosslinking agents are di- or polygly cidyl compounds such as ethylene glycol diglycidyl ether, the implementation products of polyamidoamines with epichlorohydrin and 2-oxazo lidinone, which reacts both with carboxyl groups with crosslinking can.

The crosslinking agent solution is preferably applied by application spray a solution of the crosslinker in conventional reaction mixing or mixing and drying systems. After spraying on the Crosslinker solution can follow a temperature treatment step preferably in a downstream dryer, at a Temperature between 80 and 230 ° C, preferably 80-190 ° C, and esp preferably between 100 and 160 ° C, over a period of 5 minutes to 6 hours, preferably 10 minutes to 2 hours and particularly preferably 10 minutes to 1 hour, both gaps products as well as solvent components can be removed. However, drying can also take place in the mixer itself Heating the jacket or blowing in a preheated support gases.

In a particularly preferred embodiment of the invention, the hydrophilicity of the particle surface polymer (b) is additionally modified by the formation of complexes. The complexes are formed on the outer shell of the hydrogel particles by spraying on solutions of di- or polyvalent metal salt solutions, the metal cations being able to react with the acid groups of the polymer to form complexes. Examples of divalent or polyvalent metal cations are Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Sc ³⁺ , Ti ⁴⁺ , Mn ²⁺ , Fe ^{2 + / 3 +} , Co ²⁺ , Ni ²⁺ , Cu ^{+ / 2 +} , Zn ²⁺ , Y ³⁺ , Zr ⁴⁺ , Ag ⁺ , La ³⁺ , Ce ⁴⁺ , Hf ⁴⁺ , and Au ^{+ / 3 +} , preferred metal cations are Mg ²⁺ , Ca ^{2 +} , Al ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ and La ³⁺ , and particularly preferred metal cations are Al ³⁺ , Ti ⁴⁺ and Zr ⁴⁺ . Of the metal cations mentioned, all salts are suitable which have sufficient solubility in the solvent to be used. Water, alcohols, DMF, DMSO and mixtures of these components can be used as solvents for the salts. Water and water / alcohol mixtures such as water / methanol or water / 1,2-propanediol are particularly preferred.

Spraying the salt solution onto the particles of the hydrogel-for polymer can be used both before and after the surface post-crosslinking of the particles. Especially before In preferred processes, the salt solution is sprayed on in the same way Chen step with spraying the crosslinker solution, both Solutions separately one after the other or simultaneously via two nozzles be sprayed on, or crosslinker and saline solution combined over a nozzle can be sprayed on.

The introduction of the organic iodine compound into the absorbent Mixture can already be produced during the production of the polymer (b) respectively. So it can be before, during or after the polymerization be added. Liquid iodine compounds are preferred applied together with the surface post-crosslinking solution. If appropriate, the iodine compound is preferably added as a solution applied to the surface post-crosslinking step, for example sprayed on by means of a nozzle. Are also preferred organic iodine compound, especially as a solid mixed with the powder of the hydrogel-forming polymer.

The resulting hydrogel-forming polymer contains the organic iodine compound evenly depending on the time of addition distributed or reinforced on its surface. Particularly preferred becomes hydrogel, the surface of which with the organic iodine was treated.

In a preferred embodiment of the invention, the absorbent mixture phenoxyethanol as additive. The Concentration of phenoxyethanol is 0.001 to 5% by weight, preferably 0.01 to 2% by weight, in particular 0.05 to 1% by weight based on the total weight of the absorbent mixture. The Phenoxyethanol can be introduced similarly to the iodine compound become.

In a further preferred embodiment, borates, preferably sodium tetraborate and / or boric acid of the mixture in Quantities from 0.01 to 10% by weight, preferably 0.1 to 5% by weight  based on the total mixture of the absorbent mixture puts.

Absorbent mixtures with a pH of 3 are preferred and 7, preferably from 4 to 6 and in particular from 4.5 to 6 be wearing.

Optionally, a further modification of the particles made of polymer (b) can be carried out by admixing finely divided inorganic solids, such as, for example, silica, bentonite, aluminum oxide, titanium dioxide and iron (II) oxide, which further enhances the effects of surface treatment. The addition of hydrophilic silica or of aluminum oxide with an average size of the primary particles of 4 to 50 nm and a specific surface area of 50-450 m ² / g is particularly preferred. The addition of finely divided inorganic solids takes place before the surface modification by crosslinking / complex formation, but can also be carried out before or during these surface modifications.

The absorbent mixtures according to the invention show good fungi zide and bactericidal properties. The containing incontinence articles show good skin tolerance.

The present invention further relates to the use of the organic iodine compounds mentioned above in incontinence articles.

The present invention further relates to incontinence articles comprising

• A) an upper liquid-permeable cover
• B) a lower liquid impermeable layer
• C) containing a core located between (A) and (B)
  • 1. 30-100% by weight of the absorbent mixture according to the invention
  • 2. 0-70% by weight of hydrophilic fiber material
• D) optionally one immediately above and below of the core (C) tissue layer and
• E) if appropriate, an opening located between (A) and (C) take shift.

Incontinence articles include incontinence pads and incontinence pants for adults as well as diapers for babies too understand.

The liquid-permeable cover is the layer that has direct skin contact. The material are over Liche synthetic and semi-synthetic fibers or films like Polyester, polyolefins, rayon or natural fibers such as tree wool. With non-woven materials, the fibers are in the re gel connected by binders such as polyacrylates. Preferred Materials are polyester, rayon and their blends, polyethylene and polypropylene.

The liquid-impermeable layer (B) generally exists from a film made of polyethylene or polypropylene.

In addition to the mixture (C1) according to the invention, the core (C) contains hydrophilic fiber material (C2). Hydrophilic is to be understood hen that aqueous liquids move quickly over the fiber divide. Usually the fiber material is cellulose, modified graced cellulose, rayon, polyester such as polyethylene terephthalate. Cellulose fibers such as cellulose are particularly preferred. The Fibers usually have a diameter of 1-200 µm before pulls 10-10 µm. In addition, the fibers have a minimum length of 1 mm.

The proportion of the hydrophilic fiber material based on the total amount of the core is preferably 20-70% by weight, especially before add 40-70 wt .-%.

The structure and shape of diapers is well known and described for example in EP-A-0 316 518 and EP-A-0 202 127 ben.

The following examples are intended to explain the invention in more detail.

Description of the test methods Measurement of the pH

100 ml 0.9% by weight NaCl solution is in a 150 ml beaker using a magnetic stirrer at moderate speed stirs without air being drawn into the solution. To this Solution are given 0.5 ± 0.001 g of absorbent mixture and Stirred for 10 minutes. After 10 minutes the pH of the Solution measured using a pH glass electrode, the value  is only read when it is stable, but at the earliest after 1 minute.

Determination of the microbicidal effectiveness

1 g absorbing mixture is mixed with 100 ml synthetic urine replacement solution and 0.1 ml germ solution (approx. 1-5 × 10 ⁸ CFU per ml germ suspension) is added. The synthetic urine replacement solution contains 0.64 g CaCl ₂ , 1.14 g MgSO ₄ × 7 H ₂ O, 8.20 g NaCl and 20.0 g urea per 1000 ml demineralized water. The contaminated test solution is incubated at 37 ° C. with shaking at 100 rpm in a water bath. At the time of 0 minutes, after 6 and 23 hours, 10 ml of contaminated test solution are mixed with 90 ml of caso broth and inactivating substances. 1 ml of the inactivation broth is mixed with Caso agar and 0.1 ml of inactivation broth is spatulated out on Caso agar + HLT.

example 1

In a butt well insulated by foamed plastic material a 10-liter capacity capacity of 3600 g demineralized water and 1400 g of acrylic acid. Now done the addition of 7.5 g tetraallyloxyethane and 1.7 g 4-methylphenyl diiodomethyl sulfone. At a temperature of 4 ° C Initiators consisting of 2.2 g of 2,2'-azobisamidino-propanedihy drochloride, dissolved in 20 g of deionized water, 4 g of potassium peroxo disulfate, dissolved in 150 g demineralized water and 0.4 g ascorbin acid, dissolved in 20 g of deionized water, added in succession and stirred. The reaction solution is then ste without stirring henhen, by starting polymerization, in their As the temperature rises to approx. 92 ° C, a firm gel arises. This is then mechanically crushed and by adding 25% by weight sodium hydroxide solution to a pH of 5.5 set. The gel is then dried, ground and made up sieved a grain size distribution of 100-850 microns. 1 kg of this dried hydrogel is in a ploughshare mixer with a Solution consisting of 25 g of deionized water, 40 g of methanol and 20 g of a 15% by weight aqueous solution of a polyamidoamine Epichlorohydrin adduct (RETEN 204 LS from Hercules) sprayed and then annealed at 140 ° C for 60 minutes. The micro bicidal effectiveness of the product described here determined (Table 1):

Table 1

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

Example 2

In a butt well insulated by foamed plastic material a 10-liter polyethylene container is 3500 g demineralized water and 1500 g of acrylic acid. Now done the addition of 4.5 g of methylene bisacrylamide. At one temperature of 2 ° C the initiators, consisting of 2.0 g of 2,2'-Azobisa midino propane dihydrochloride, dissolved in 20 g of deionized water, 4.4 g of potassium peroxodisulfate, dissolved in 150 g of deionized water such as 0.8 g of ascorbic acid, dissolved in 20 g of deionized water admitted to each other and stirred. The reaction solution is thereupon left there without stirring, with polymeri sation, in the course of which the temperature increases to approx. 98 ° C increases, a solid gel is formed. This is then mecha nisch crushed and by adding 50 wt .-% sodium hydroxide solution adjusted to a pH of 4.5. The gel is then dried net, ground and to a grain size distribution of 100-850 µm sieved. 600 g of this dried hydrogel is in one Petterson & Kelly mixer with a solution consisting of 0.2 g Ethylene glycol diglycidyl ether, 0.8 g of 4-methylphenyldiiodomethyl sulfone, 3.0 g phenoxyethanol, 22.5 g isopropanol and 22.5 g ent sprayed salted water and then for 45 minutes at 120 ° C annealed. The microbicidal effectiveness of the present description NEN product was determined (Table 2).  

Table 2

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

Example 3

In a well insulated by foamed plastic material Polyethylene container with a capacity of 30 l 14340 g of demineralized water and 30 g of pentaerythritol triallyl ether submitted as a copolymerization crosslinker, 5170 g of sodium bi carbonate suspended in it and slowly 5990 g of acrylic acid metered in that overexposure to the reaction solution is avoided is, which depends on a temperature of about 3-5 ° C cools. At a temperature of 4 ° C, the initiators, 6.0 g 2,2'-Azobisamidinopropanedihydrochlorid dissolved in 60 g desalted Water, 12 g potassium peroxodisulfate, dissolved in 450 g desalinated Water and 1.2 g of ascorbic acid, dissolved in 50 g of desalted water water, added one after the other and stirred well. The reaction solution is then left without stirring, with a settling polymerization, in the course of which the temperature drops to approx. 85 ° C, a gel is formed. This is then in transferred a kneader with 16 g of 4-methylphenyl-diiodomethylsul fon and 180 g of sodium tetraborate mixed, kneaded homogeneously, zer crushed, dried in an air stream at 170 ° C, ground and ge seven. 1 kg of this product was in a ploughshare mixer a solution of 2 g polyglycerol polyglycidyl ether (Denacol EX-512 from Nagase Chemicals Ltd.), 0.3 g citric acid, 60 g ent salted water and 40 g of 1,2-propanediol and then sprayed Annealed at 150 ° C for 40 minutes. The microbicidal effectiveness of the product described here, which has a pH of 6.0, was determined (Table 3).  

Table 3

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

Comparative Example 1

The procedure is as in Example 1, but the monomer solution no 4-methylphenyl-diiodomethyl sulfone added. The The microbicidal activity of the product was determined (Table V1).

Table V1

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

The hydrogels obtained according to Examples 1 to 3 are characterized in In contrast to the hydrogel obtained in the comparative example excellent microbicidal effectiveness and are therefore in excellent as an absorbent for water and aqueous Liquids, especially body fluids, such as. B. Suitable for urine or blood, for example in hygiene articles such as e.g. B. Baby and adult diapers.

Example 4

In a butt well insulated by foamed plastic material a 10-liter capacity capacity of 3600 g demineralized water and 1400 g of acrylic acid. Now done the addition of 7.5 g of tetraallyloxyethane and 1.4 g of 3-iodo-2-propy nylbutyl carbamate. At a temperature of 4 ° C the Initia  gates, consisting of 2.2 g of 2,2'-azobisamidino-propanedihydrochlo rid, dissolved in 20 g of deionized water, 4 g of potassium peroxodisulfate, dissolved in 150 g of demineralized water and 0.4 g of ascorbic acid, ge dissolves in 20 g of deionized water, added one after the other and ver stirs. The reaction solution is then standing without stirring let, by the onset of polymerization, in the course the temperature rises to approx. 92 ° C, a firm gel ent stands. This is then crushed mechanically and by Add 25% by weight sodium hydroxide solution to a pH of 5.5 set. The gel is then dried, ground and placed on a Grain size distribution of 100-850 µm sieved. 1 kg of this ge dried hydrogel is in a ploughshare mixer with a Solution consisting of 25 g of deionized water, 40 g of methanol and 20 g of a 15% by weight aqueous solution of a polyamidoamine Epichlorohydrin adduct (RETEN 204 LS from Hercules) sprayed and then annealed at 140 ° C for 60 minutes. The micro bicidal effectiveness of the product described here determined (Table 4).

Table 4

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

Example 5

In a butt well insulated by foamed plastic material a 10-liter polyethylene container is 3500 g demineralized water and 1500 g of acrylic acid. Now done Add 4.5 g of methylene bisacrylamide. At a temperature of 2 ° C the initiators, consisting of 2.0 g of 2,2'-azobisami dino-propanedihydrochloride, dissolved in 20 g of deionized water, 4.4 g of potassium peroxodisulfate, dissolved in 150 g of deionized water such as 0.8 g of ascorbic acid, dissolved in 20 g of deionized water admitted to each other and stirred. The reaction solution is thereupon left there without stirring, with polymeri sation, in the course of which the temperature increases to approx. 98 ° C increases, a solid gel is formed. This is then mecha nisch crushed and by adding 50 wt .-% sodium hydroxide solution  adjusted to a pH of 4.5. The gel is then dried net, ground and to a grain size distribution of 100-850 µm sieved. 600 g of this dried hydrogel is in one Petterson & Kelly mixer with a solution consisting of 0.2 g Ethylene glycol diglycidyl ether, 0.6 g 3-iodo-2-propynylbutylcarba mat, 3.0 g phenoxyethanol, 22.5 g i-propanol and 22.5 g desalted sprayed water and then ge for 45 minutes at 120 ° C. tempered. The microbicidal effectiveness of what is described here Product was determined (Table 5).

Table 5

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

Example 6

In a well insulated by foamed plastic material Polyethylene container with a capacity of 30 l 14340 g of demineralized water and 30 g of pentaerythritol triallyl ether submitted as a copolymerization crosslinker, 5170 g of sodium bi carbonate suspended in it and slowly 5990 g of acrylic acid metered in that overexposure to the reaction solution is avoided is, which depends on a temperature of about 3-5 ° C cools. At a temperature of 4 ° C, the initiators, 6.0 g 2,2'-Azobisamidinopropanedihydrochlorid dissolved in 60 g desalted Water, 12 g potassium peroxodisulfate, dissolved in 450 g desalinated Water and 1.2 g of ascorbic acid, dissolved in 50 g of desalted water water, added one after the other and stirred well. The reaction solution is then left without stirring, with a settling polymerization, in the course of which the temperature drops to approx. 85 ° C, a gel is formed. This is then in transferred a kneader with 18 g of 3-iodo-2-propynylbutyl carbamate and 180 g of sodium tetraborate added, kneaded homogeneously, mashed nert, dried in an air stream at 170 ° C, ground and sieved. 1 kg of this product was in a ploughshare mixer with a Solution of 2 g polyglycerol polyglycidyl ether (Denacol EX-512 from Nagase Chemicals Ltd.), 0.3 g citric acid, 60 g desalted water  water and 40 g of 1,2-propanediol and then sprayed for 40 minutes annealed at 150 ° C for a long time. The microbicidal effectiveness of this described product, which has a pH of 6.0 has been determined (Table 6).

Table 6

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

Comparative Example 2

The procedure is as in Example 4, but the monomer solution no 3-iodo-2-propynylbutyl carbamate added. The micro The bicidal activity of the product was determined (Table V2).

Table V2

Content of colony-forming units (CFU) per ml test solution depending on the incubation period

The hydrogels obtained according to Examples 4 to 6 are characterized in In contrast to the hydrogel obtained in Comparative Example V2 characterized by excellent microbicidal effectiveness and are therefore excellent as an absorbent for water and aqueous liquids, especially body fluids, such as e.g. B. urine or blood suitable, for example in hygiene articles such as B. baby and adult diapers and the like.

Claims (9)

1. Absorbent mixture containing

• a) an organic iodine compound and
• b) a hydrogel-forming polymer,

the proportion of the iodine compound being 0.001 to 5% by weight of the hydrogel-forming polymer. 2. Absorbent mixture according to claim 1, consisting of

• a) an organic iodine compound and
• b) a hydrogel-forming polymer

and optionally additives customary for hydrogel. 3. Absorbent mixture according to claim 1 or 2, characterized ge indicates that the hydrogel-forming polymer crosslinks t polymer from acid-bearing monoethylenic unsaturated monomers, optionally before or after Polymerization converted into their alkali or ammonium salts and 0-40 wt .-% based on its total weight no monoethylenically unsaturated acid groups Is monomers. 4. Absorbent mixture according to claims 1 to 3, characterized in that the hydrogel-forming polymer is a ver crosslinked polymer of monoethylenically unsaturated C ₃ -C ₁₂ carboxylic acids and / or their alkali metal or ammonium salts. 5. Absorbent mixture according to claims 1 to 4, characterized characterized in that the organic iodine compound 3-iodo-2-propynyl-N-butyl carbamate or 4-methylphenyl diiod is methyl sulfone. 6. Use of organic iodine compounds in incontinence articles.   7. Hydrogel-forming polymer, the surface of which ranges from 0.001 to 5 wt .-% organic iodine compound based on the polymer was treated. 8. Use of absorbent mixtures, according to the An Proverbs 1 to 5 in incontinence articles. 9. Including incontinence articles

• A) an upper liquid-permeable cover
• B) a lower liquid impermeable layer
• C) containing a core located between (A) and (B)
  • 1. 30-100 wt .-% of an absorbent mixture according to claims 1-5
  • 2. 0-70% by weight of hydrophilic fiber material
• D) optionally a tissue layer located immediately above and below half of the core (C) and
• E) optionally a receiving layer located between (A) and (C).