DE4206856C2 - Polymer composition, absorbent material composition, their preparation and use - Google Patents

Description

The invention relates to a polymer composition and in particular special absorption materials, mainly after based on growing raw materials, and thus basically are biodegradable. Due to the predominantly native Origin, the absorber contain no or much lower Amounts of residual monomers as polyacrylate-based absorbers. The polymer compositions and absorbers according to the invention have a comparatively high absorption capacity and quantity speed for water and aqueous solutions, show no Gel blocking tendency (gel blocking: on contact with water glue the outer layers of the absorber and prevent further penetration of the liquid into the absorber) and are mechanically stable (in terms of segregation in the one individual components). When swollen, they separate into individual particles, they are not watery and have a great deal high gel stability on. The invention relates to a method for their preparation and their use for the absorption of Water, aqueous solutions and body fluids in hygiene and animal hygiene articles, in packaging materials for Meat and fish, in culture vessels and for Bodenverbesse tion and as cable sheathing.

Most of the absorption materials used today, Also called superabsorbents, which are able to in short Time to absorb large amounts of fluids (water, urine), represent primarily weakly crosslinked polyacrylates and are therefore not based on renewable resources and are comparatively insufficient or not bio at all logically degradable.  

In an effort to produce superabsorbents from renewable raw materials was, as described in DE-C-26 12 846, acrylic acid on polysaccharides, such as. B. on corn starch on grafted. However, only small amounts of Po lysaccharides (up to a maximum of 25%) are used, otherwise drastic deterioration of the absorption properties to be obtained.

Similarly, by the incorporation of polysaccharides into the Polymerization gel of polyacrylates, as in DE-OS'en 40th 29 591, 40 29 592 and 40 29 593, the poly acrylates only up to max. 25% will be replaced without a German Weak deterioration of capacity and other egg properties of the resulting superabsorbents, although in addition various adjuvants, such as fibers and z. B. Aluminum crosslinkers are added. The polysaccharides are seen as building blocks for the absorbers to biological to obtain degradable units.

The DE-PS 31 32 976 describes the mixing of polyacrylic acid with polysaccharides in powder form and in solution, the shell of the absorber particles of the mixtures with Aluminiumver network such as Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ crosslinked. Accordingly, even with this method, no superabsorbent bar can be represented, which consist of more than 60% renewable raw materials.

In the hitherto described according to the current state of the art The polysaccharides have no decisive decision which contribution as absorption component.  

Numerous patent publications such as DE-OS 26 34 539 describe the preparation of carboxymethyl cellulose Absor bern, that is, of materials that are biodegradable in principle bar, by crosslinking the carboxymethylcellulose with various crosslinkers in the aqueous system. These absorbers however, show a strong gel blocking.

US Pat. No. 4,959,341 describes the preparation of a carboxymethylcellulose-based absorber,
which consists of a mixture of carboxymethylcellulose, Cellulo sefasern, a hydrophobic component and Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ as a crosslinker, wherein the aluminum crosslinker causes crosslinking of carboxymethylcellulose during liq sigkeitsaufnahme.

These absorbers have good absorption properties but block phenomena. In addition, these absorbers by mecha nische loads, such as screening or promotion, easily ent mixes so that they no longer exist as a homogeneous product which severely limits their potential applications.

In EP-B 0 201 895 is also the production of a Absorbers based on carboxymethylcellulose described ben. However, in the manufacture of this absorber in worked an aqueous solution in which the carboxymethyl cellulose is present only in low concentration. Farther become in the production of larger amounts of organic Lö needed. The preparation of this carboxymethyl Cellulose absorber also requires a lot of time. The absorbers themselves show block phenomena and a low one Gel strength.  

The present invention was based on the object Pathways a polymer composition and absorption material composition (hereinafter abbreviated absorber) not providing the above-described defects and which has the following properties:

• a) The absorber should predominantly consist of components native Ur There are also leaps and thus also biological be degradable.
• b) The absorber should have a high mechanical strength wise, they may sieve or z. B. at a Screw conveyance not in their individual components separate.
• c) The absorbers should have a comparatively high absorption rate speed and capacity for water and aqueous Own solutions.
• d) The content of residual monomers should be significantly lower than conventional absorbers based on Polyacrylates.
• e) The absorbers are in the swollen state a very high Have gel stability; while the absorber grains separated, present in individual particles.
• f) They must not tend to gel blocking.

According to the solution of this task is carried out by a Polymer composition and an absorbent composition consisting essentially of four components:

• - a component A, which is based on special renewable raw material based materials
• - a component B, which consists of a special wasserquellba ren polymers
• - a matrix and
• - an ionic or covalent crosslinker as well
• - optionally with the addition of an antiblocking agent.

The present invention thus relates to a polymer composition, consisting essentially of
70-99.9 wt .-% of a component A based on water-soluble and / or water-swellable polymers based on polysaccharides and their derivatives, which may have been modified by crosslinking,
0.1-30% by weight of a component B based on water-swellable synthetic polymers and / or copolymers based on (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, maleic acid (- hydride), itaconic acid (anhydride), fumaric acid, vinylsulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and the amides, N-alkyl derivatives, the N, N'-dialkyl derivatives, the hy droxylgruppen-containing esters and the amino group-containing esters these polymerizable acids, wherein 0-98% of the acid groups of these acids are neutralized, and wherein these polymers and / or copolymers are crosslinked by at least one at least bifunctional compound, as polymeric components, and 0.1-30 wt .-%, based on these polymeric components, at least one matrix material having a melting point or softening point below 180 ° C to prevent segregation and gel blocking, 0.001-10 wt .-%, based on this polymeric component nten, at least one ionic or covalent crosslinker, and 0- 50 wt .-%, based on these polymeric components, at least one antiblocking agent based on natural and / or synthetic fibers or other materials with a high surface area.

Furthermore, the present invention relates to an absorptive Onsmaterialzusammensetzung, from the above Components and a drug-containing depot material composition of the above kind containing the active ingredient delayed release.

It was surprisingly found that a slight Addition of component B to component A is a distinct Improvement of the absorption properties causes. Since only ge additions of component B are necessary, is thus the Residual monomer content of z. As acrylic acid of such Absor bers significantly lower than absorbers on Polyacrylatba sis.

Furthermore, it was surprisingly found that by the Zu Set of a solid, which serves as a matrix for the absorber system acts, in combination with the polymer absorbent, a mixture of components A and B, and an ioni rule crosslinker and optionally an antiblocking agent, an Ab sorption agent can be produced that a high Aufnahmege speed and capacity for water and aqueous solutions and improved mechanical strength in terms has the segregation of the individual dry particles. Furthermore, the gels of this absorber system are separated into single particles before.  

In addition, these absorbers surprisingly show in Kom Combination with the above properties, a gel starch, which is significantly higher than that of absorbers, the Build on polyacrylic acid-based.

As component A are water-soluble and water-swellable Po Polymers based on polysaccharides and their derivatives suitable, such as guar, carboxymethylguar, xanthan, alginates, Gum arabic, hydroxyethyl or hydroxypropyl cellulose, Carboxymethylcellulose and other cellulose derivatives, starch and starch derivatives such as carboxymethyl starch and mixtures of the individual polysaccharides. The preferred polymers are Starch, guar and cellulose as well as the anionic derivatives of Starch, guar and cellulose, with carboxymethyl cellulose represents particularly preferred material.

The listed polymers of component A can by a Crosslinking can be modified to increase their water solubility reduce and achieve better swelling properties. The Crosslinking can take place either throughout the polymer or but only on the surface of the individual polymer part kel.

The reaction of the polymers can be carried out with ionic crosslinkers such as z. As calcium, aluminum, zirconium, iron (III) - and titanium Connections take place. Likewise, the implementation with polyfunk tional carboxylic acids such as citric acid, mucic acid, wine acid, malic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, with alcohols such as polyethylene glycols, glycerol, Pentaerythritol, propanediols, sucrose, with carbonic acid esters such as ethylene and propylene carbonate, with amines such as polyoxypro pylenamine, with epoxy compounds such as ethylene glycol diglyci  dyl ether, glycol di or triglycidyl ether and epichlorohydrin, with acid anhydrides such as succinic anhydride and maleic acid anhydride, with aldehydes and polyfunctional (activ th) olefins such as bis (acrylamido) acetic acid and methylene bisacrylamide possible. Likewise come derivatives of the mentioned Classes of compounds as well as heterofunctional Ver bonds with different functional groups of the above mentioned classes of compounds.

As component B are water-swellable synthetic polymers or copolymers based primarily on (meth-) Acrylic acid and further based on (meth) acrylni tril, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid, maleic anhydride, itaconic acid, Ita Acetic anhydride, fumaric acid, vinylsulfonic acid, 2-acrylic amido-2-methylpropanesulfonic acid, as well as the amides, their N- Alkyl and N, N'-dialkyl derivatives, hydroxyl-containing esters and amino group-containing esters of the polymerizable Säu suitable. Preference is given to crosslinked, partially neutrali sierte polyacrylates.

It can up to 98%, preferably 50-80% of Säuregrup be neutralized.

The polymers can be replaced by an at least bifunctional Crosslinker be crosslinked.  

The preparation of these above polymers is carried out according to known methods (DE-C 27 06 135, DE-A 40 15 085). A be particularly preferred material as component B represent poly acrylates, e.g. B. from the chemical factory Stockhausen GmbH produced FAVOR® types, the subject of DE-A 40 15 085 are.

As a matrix organic solids are suitable, which are under 180 ° C melt or soften and preferably at Raumtem have a soft consistency, such. B. Triglyce rinmonostearat or special wax esters. Likewise, are high viscous liquids such. B. castor oil suitable.

Preferably suitable as a matrix polycaprolactones, such as TONE 0230 and 0240 from Union Carbide, which also modified can be, such as B. by reaction with maleic acid hydride.

Through the matrix, the absorber system presumably gets through chemical and / or physical interactions a higher mechanical strength, eliminating the segregation of the individual components through transport processes, such. B. by means of a Screw conveyor, or greatly reduced by Absiebvorgänge becomes. This can produce an absorbent which not only has high absorption values, but after ei ner confectioning or after incorporation in his Verwen as a more homogeneous and therefore more effective system is present.

In addition, the embedding of the absorbent material in the matrix surprisingly a significant reduction or a total elimination of Gelblocking, thus is ensures a high absorption rate throughout the absorber guaranteed. Furthermore, the crosslinker is solidified by the matrix  fixed on the surface of the individual absorber particles. The granulation of superabsorbent fine dusts by Agglomeration aids is used in the examples of DE-PS 37 41 157 and DE-PS 39 17 646 described. The so produced th products have a high absorption rate for Water and aqueous solutions. However, these products exist only polyacrylates and therefore are relatively unzu reaching or not at all biodegradable. The agglo Merisierungsmittel serve only for granulation of a product and in no case as a matrix material.

The anti-blocking agents also reduce gel blocking; So they cause a faster and better fluid and ensure that the gels separate, ie. H. in individual particles are present.

Suitable anti-blocking agents are known (cf. DE-PS 31 41 098 and DE-PS-33 13 344) fiber materials and on These materials have a large surface area.

The fibers may be natural or synthetic fibers, such as B. wool, cotton, silk and cellulose fibers, or Polyamide, polyester, polyacrylonitrile, polyurethane fibers, Fibers of olefins and their substitution products as well Polyvinyl alcohol fibers and their derivatives. Examples of anor ganic materials are bentonites, zeolites, aerosils and Activated carbons.

Suitable crosslinkers are compounds which are the above be described polymers in a state in which the Water solubility is reduced, improves the pumping speed and the block phenomena are reduced.  

Suitable ionic crosslinkers are metal compounds which interact with the functional groups of the polymers can occur. Particularly preferred are magnesium, calcium, Aluminum, zirconium, iron, titanium and zinc compounds, which have a very good solubility in water, like the salts of carboxylic acids and inorganic acids.

Preferred carboxylic acids are acetic acid, lactic acid, salicyl acid, propionic acid, benzoic acid, fatty acids, malonic acid, Succinic acid, glutaric acid, adipic acid, citric acid, Tartaric acid, malic acid and mucic acid.

Preferred inorganic anions are chlorides, bromides, Hy sulfates, phosphates, borates, nitrates, hydrosulfates gencarbonates and carbonates.

Furthermore, organic compounds are suitable, the mehrwer containing such metals as acetylacetonates and alcoholates, such as B. Fe (acac) ₃, Zr (acac) ₄, Ti (OBu) ₄ and Zr (o-prop) ₄.

The water-soluble crosslinker causes a crosslinking of Components A and B, both between each other and between each other, especially on the surface, which, as in the DE-OS 31 32 976, DE-C 26 09 144 and US-A 4,959,341 be is written, the absorption properties improved who the.

As covalent crosslinkers are polyfunctional carboxylic acids, Alcohols, amines, epoxy compounds, carboxylic anhydrides and Aldehydes, and their derivatives suitable. examples are Citric acid, mucic acid, tartaric acid, malic acid, malon acid, succinic acid, glutaric acid, adipic acid, polyethylene glycols, glycerin, propanediols, polyoxypropyleneamines, epi chlorohydrin, ethylene glycol diglycidyl ether, glycol diglycidyl  ether, succinic anhydride, maleic anhydride, ethylene carbonate and propylene carbonate suitable. Likewise come naturally derivatives of the compounds mentioned, as well as heterofunctional compounds with different functio groups of the above classes of compounds.

The proportion of component A to the ratio of component A to Component B is 70-99.9% by weight, preferably 75-90 Wt .-%. The proportion of component B is 0.1-30 wt .-% before preferably 10-25% by weight.

The addition, even in small amounts, of component B causes a strong improvement in the absorption properties, before all of the sucking power. This can be a surprisingly significant slight improvement in absorption properties pure carboxymethyl cellulose material (CMC material) achieved become.

The amount of anti-blocking agent is preferably between 0.5 and 50 wt .-%, particularly preferably 5-15 wt .-%, based on components A and B.

The amount of crosslinker in the absorber is 0.001-10% by weight, preferably 3-7 wt .-%, based on the components A and B.  

The addition of matrix material based on the components A and B is between 0.1-30% by weight, preferably between 2.5 and 7.5% by weight.

The matrix prevents the absorption from falling apart materials, as is the case with pure physical mixtures z. As observed in US-A 4,952,550 and prevented additionally a gel blocking.

The preferred preparation of the absorbent material is described below.

For the production of the absorbent according to the invention the component A and the component B physically in dry form mixed at room temperature. This material comes with the anti-blocking agent and the matrix component mixed until a homogeneous mixture is present. The mixture The components are made in suitable mixers such as screws mixer, fluid bed mixer, disc mixer or belt mixer.

The heat treatment takes place at 25-180 ° C, preferably at 100-120 ° C instead. The heating time is 5-60 minutes th, preferably 20-40 minutes. For heat treatment of Product become ordinary dryers or stoves (eg Disc dryer, belt dryer, fluid bed dryer or infrared dryer).

Subsequently, the ionic crosslinker, preferably Aluminum dihydroxyacetate stabilized with boric acid Room temperature incorporated until a homogeneous mixture ent stood is. For fixing the crosslinker through the matrix is again at 25-180 ° C, preferably at 50-80 ° C, for Heated for 5-60 minutes to melt the matrix material.  

The components A and B can be sieved before mixing be, preferably in the range of 90-630 microns.

The incorporation of the matrix components is preferably carried out at room temperature, but the matrix component can also be used as Melt be used.

The mixture can with a preferential before the heat treatment Wise water / isopropanol mixture are added to a Solubilizer to have a thermal modification the component A, ie a polysaccharide and not from Polyacrylic acid, among themselves, as well as with the Matrixkompo component and component B in the peripheral areas of the compo A, which has a positive effect on the absorbency of the Absorption material affects. Instead of the water / isopropanol Mixture can also use water and other mixtures of water water-soluble organic solvents are used.

In EP-PS 0 083 022, the crosslinking of an absorber described which consists of polyacrylic acid, with crosslinking agents, containing at least two functional groups and in the Able to react with the carboxyl groups of the polyacrylate yaw. The reaction takes place on the surface of the absorber particles.

DE-PS 33 14 019 and DE-PS 35 23 617 also describe the Surface crosslinking of polyacrylates using Vernet which possess at least two functional groups. in the In contrast to the absorbers according to the invention are in these Patents only modifications of polyacrylates, but not of polysaccharides, described in the shell, but causing in no case absorbers are obtained which are sufficiently biolo are degradable.

The incorporation of the ionic crosslinker can also be directly in the physical mixture component A, component B, anti- Blocking agent and matrix material take place, whereupon  25-180 ° C, preferably at 100-120 ° C, for 5-120 minutes th, preferably for 20-60 minutes is heated.

The solvent step described above may be used in this Procedure before or after the crosslinker incorporation.

The covalent crosslinker may alternatively and in addition to the ionic crosslinker to the polymer mixture before or after Matrix addition can be added.

The covalent crosslinker is given in a preferably if dissolved alcohol / water mixture and the polymer mixture added dropwise with rapid stirring. The amount of solvent is between 1 and 10% based on the polymer mixture. It is then heated to 25-180 ° C for 5-120 minutes. As a solvent, water and mixtures of water with water-soluble organic solvents are used.

The absorbent material according to the invention shows a good Biodegradability to products on one Polyacrylsäurebasis based, at one, compared to previously be knew absorbing materials on a native basis strongly ver improved absorption and absorbency for a 0.9% cook salt solution, at a surprisingly very high gel strength.  

Gel strength of some absorbers according to the invention and some well-known absorber

Product name Gel strength (10 Hz) (N / m²) absorber according to the invention Superabsorber from example 3  10000 Superabsorber from Example 4  10000 Superabsorber from Ex. 10  10000 Superabsorber from Ex. 11  10000 Superabsorber from Ex. 14  10000 Superabsorber from Ex. 15  10000 well-known absorbers @ Product A 2450 Product B 4200 Product C 3500 Product D 2700 Products 4950 Product F 3700 Product G 1575

Products A, B, C, D, F and G:
crosslinked, partially neutralized polyacrylates
Products:
crosslinked, partially neutralized polyacrylate starch graft polymer.

Furthermore, the mechanical strength (in terms of Entmi Schung in the individual components) compared to the previously be written on renewable raw materials based Absor significantly improved.

The polymer composition according to the invention can in particular as absorbent material as fiber, film, powder or granu lat used to water or aqueous liquids, like urine and blood, and is therefore particularly for use in diapers, tampons, surgical products, Cable sheathing, culture vessels, packaging materials for Meat or fish and absorbent garments suitable.

In addition, the material as a storage medium for successive Release of active substances, such as medicines, pesticides (US 4,818,534, US 4,983,389, US 4,983,390, US 4,985,251) and Fragrances suitable, with the advantage that the memory medium degradable. This results in another Advantage that the drug is completely released.

The active substance-containing depot materials can by Absorp tion, preferably concentrated, aqueous or wasserhal tiger solutions in the largely dry absorber and possibly whose re-drying is produced.

The active ingredient can also be used directly or as a solution or as a disper at any preliminary stages of the manufacturing process of the Absorber composition may be added.  

The active substance-containing depot materials are in powder form or as a dispersion in hydrophobic media containing dispersions stabilizing agents such as emulsifiers or stabilizers contain or in mixture with other substances such as Polysaccharides used.

For example, by the addition of such Bakterizidhalti ger depot materials to cellulose, guar or starch produk or their derivatives, such as carboxymethylcellulose, in de ren storage and application in aqueous media, the degradation of the prevents these substances for a long time and whereby the depot effect larger amounts of free drug in the Solution can be avoided.

test methods Teabag Test (TBT)

To determine the absorbency, a teabag Test completed. The test solution was an aqueous 0.9% NaCl solution used.

0.2 g of a test substance (screened between 90 and 630 μm), which was weighed in a teabag, allowed 10 or 30 Swell for a few minutes in the test solution. After five minutes Ab drops  (Maximum) was in a centrifuge, such. B. in one commercially available spin dryer, centrifuged at 1400 rpm. The fluid intake was determined gravimetrically and converted to 1 g of substance. (Retention value).

Absorption under load (AUL)

To determine the liquid absorption capacity under pressure, For example, absorption under load was as described in EP-A-0 339 461 written, certainly.

0.16 g of test substance (sieved between 300 and 600 microns) was allowed by capillary action for 60 minutes under pressure of 1.55 k N / m² (99.8 g / in²) swell in 0.9% NaCl solution. The fluid intake was determined gravimetrically and converted to 1 g of substance.

Gel strength (G ')

To determine the gel strength G 'of the swollen absorber, was as described in EP-A 0 339 461, proceeded.

Device: Controlled Stress Rheometer CS 100, Carri-Med Ltd. Dorking / UK.

Measuring conditions: plate-plate system, diameter 60 mm, Plate distance 2 mm, temperature 20 ° C, torque 1000-4000 μNm, amplitude 1.5-5 mrad, frequency 10.0 Hz, 28 ml 0.9% NaCl / g absorber. The information is given in N / m².  

Flow test (FT)

The flow test was used to determine how fast the Pro the test fluid, whether it be block phenomena showed, were completely swollen and wetted everywhere were. Furthermore, it was examined whether the gels are firm, sticky or loose and separated templates.

To carry out the flow test, about 100 mg of substance placed on a water-soaked paper towel and ver follows how the water was absorbed by the products. The absorption behavior was according to the following grading scale be evaluates.

A: Attracts quickly
B: It picks up very fast
C: goes through from start to finish
D: Gel is separated after the water absorption
E: gel blocking

example 1

8 g of CMC Walocel 40000 (sodium carboxymethylcellulose, Wolff Walsrode) with 2 g Favor® 953 (crosslinked, partially neutralized sodium polyacrylate from. Stockhausen GmbH), 0.5 g of TONE 230, polyol based on caprolactone, Molge weight 1 250 g / Mol (Union Carbide), 0.5 g of Aerosil 200 (fumed silica, particle diameter: 12 nm, De Gussa) and 0.5 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ using 2 ml of isopropanol and 1 ml of water vigorously mixed and heated for 60 min at 120 ° C in the oven.
TBT (max./ret.): 45 g / g / 33 g / g; AUL = 9.9 g / g; FT: BCD

Example 2

60 g of CMC, Walocel 40000 are homogenized with 1.5 g of ethylene carbonate, 1.5 ml of water and 1.5 ml of isopropanol; The mixture is then heated in the oven at 120 ° C. for 60 minutes. 8 g of this product are mixed with 2 g of Favor® 953, 0.5 g of TONE 230, 0.5 g of fiber BE 600/30 (cellulose, diameter: 17 μm, length: 30 μm, from Ret tenmaier) and with 0, 5 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ while using 2 ml of isopropanol and 1 ml of water vigorously mixed and heated for 60 min at 120 ° C in the oven.
TBT (max./ret.) = 46 g / g / 29 g / g; AUL = 14.4 g / g; FT: BCD

Example 3

15 g of CMC, Walocel 40000 are mixed with 3 g of propylene carbonate, Homogenized 0.375 ml of water and 1.0 ml of isopropanol and at then heated to 120 ° C in the oven for 60 min.

8 g of the product thus obtained are mixed with 2.0 g Favor® 953 (Stockhausen GmbH), 0.5 g TONE 230, Union Carbide 1.0 g calcium bentonite (Südchemie) and 0.5 g Al ( OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and treated with 2 ml of isopropanol and 1 ml of water, homogenized and delt as previously thermally nachbehan.
TBT (max / ret.) = 43 g / g / 27 g / g; AUL = 14.2 g / g; FT: BCD

Example 4

The procedure is as in Example 3, but in addition 0.5 g of BE 600/30 fiber are incorporated into the product.
TBT (max./ret.) = 42 g / g / 25 g / g; AUL = 15.1 g / g; FT: BCD

Example 5

2.0 g CMC, Walocel 40000, 1 g of a polyacrylate Superabsor bers (prepared according to DE-P 40 15 085, Example 4, in the following called the SAB "A";
Ch. F. Stockhausen GmbH), 0.25 g TONE 230, 2.25 g fiber BE 600/30 and 0.25 g Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ are using Ver 2 ml of isopropanol and 1 ml Mix vigorously with water and heat for 60 minutes at 120 ° C in the oven.
TBT (max./ret.) = 33 g / g / 20 g / g; AUL = 14.8 g / g; FT: AD

Example 6

2.5 g CMC, Walocel 40000 are mixed with 2.5 g Kelzan (Xanthan Co. Kelco) and with 1 g Favor® SAB 953, 0.25 g TONE. , , , 0.25 g of fiber BE 600/30 and 0.25 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ under Ver use of 1 ml of isopropanol and 0.5 ml of water vigorously mixed ver and for 60 min at 120 ° C in Oven heated.
TBT (max./ret.) = 39 g / g / 22 g / g; AUL = 14.5 g / g; FT: CD

Example 7

2.5 g CMC, Walocel 30000, 2.5 g Natrosol 250 MR (hydroxyethyl cellulose, Aqualon), 1.0 g SAB "A", 0.5 g fiber BE 600/30, 0.25 g TONE 230, 0.25 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and 1.675 ml of water / i-propanol (1: 1) are vigorously mixed and then heated for 60 min at 120 ° C in the oven.
TBT (max./ret.) = 29 g / g / 19 g / g; AUL = 13.8 g / g; FT: ACD

Example 8

2.5 g CMC 30000, 2.5 g Natrosol 250 MR (Aqualon), 1.0 g SAB "A", 0.5 g calcium bentonite, 0.25 g TONE 230, 0.25 g Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and 1.675 ml of water / i-propanol (1: 1) are vigorously mixed and then heated for 60 min at 120 ° C in the oven.
TBT (max./ret.) = 27 g / g / 23 g / g; AUL = 13.1 g / g; FT: AD

Example 9

4.0 g of CMC, Walocel 30000, 0.1 g of citric acid, 1.0 g of SAB "A", 0.25 g of fiber BE 600/30, 0.25 g of TONE 230 and 1.675 ml of water / i-propanol ( 1: 1) are vigorously mixed and then heated ßend 30 minutes to 120 ° C in the oven. In this product, 0.25 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ incorporated and heated for 60 minutes at 50 ° C in the oven.
TBT (max / ret.) = 44 g / g / 32 g / g; AUL = 11.0 g / g; FT: ACD

Example 10

The procedure is as in Example 9, but the BE 600/30 fiber is replaced by 0.25 g of fiber (based on PES, 3.3 dtex, 0.55 mm, from Wilhelm GmbH & Co KG).
TBT (max / ret.) = 44 g / g / 34 g / g; AUL = 14.8 g / g; FT: AC

Example 11

The procedure is as in Example 8, but in addition 0.5 g of fiber BE 600/30 are incorporated.
TBT (max / ret.) = 27 g / g / 21 g / g; AUL = 13.5 g / g; FT: ACD

Examples 12, 13

4.0 g of CMC, Walocel 30000 are mixed with 1 g of SAB "A", with 0.5 g of BE 600/30 fiber, with 0.25 g of TONE 230 and with each = 0.1 g of the compound indicated in the table below homogenized with the addition of 1.675 ml of water / i-propanol (1: 1) and heated for 30 minutes at 120 ° C in the oven. In these products, 0.25 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ incorporated and heated for 60 minutes at 50 ° C in the oven.

Example 14

8 g of CMC 40000 are mixed with 2 g of Favor SAB 835 (crosslinked, partially neutralized sodium polyacrylate from Stockhausen GmbH), 0.5 g of fiber (BE 600/30 fiber, from Rettenmaier), 0.5 g of TONE 230, 1 Homogenized ml of water and 2 ml of i-propanol and then heated for 30 minutes at 120 ° C in the oven. At closing, with 0.4 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and heated for 60 minutes at 50 ° C in the oven.
TBT (max./ret.) = 45 g / g / 33 g / g; AUL = 11.4 g / g; FT: ACD

Comparative Example 1

The procedure is as in Example 14, but no Favor® SAB 835 is added.
TBT (max./ret.) = 30 g / g / 27 g / g; AUL = 10.0 g / g; FT: E
This product is unsuitable as absorbent material.

Example 15

The procedure is as in Example 14, but 0.7 g of the aluminum salt are added.
TBT (max./ret.) = 47 g / g / 36 g / g; AUL = 9.4 g / g; FT: ACD

Example 16

The procedure is as in Example 14 except that 0.5 g of the aluminum salt and 1 g of the fiber are added.
TBT (max./ret.) = 48 g / g / 34 g / g; AUL = 9.6 g / g; FT: BCD

Example 17

8 g CMC 40000, 2 g Favor SAB 835, 0.5 g fiber BE 600/30, 0.1 g Aerosil R 972 (hydrophobized, fumed silica, particle diameter: 16 nm, Degussa AG), 1 g water and 2 g Iso propanol be homogenized. Then, 0.5 g of molten, acid-terminated TONE 230 are incorporated and subsequently heated to 120 ° C. in the oven for 30 minutes. The product is homogenized with 0.6 g of the described aluminum salt and then heated for 60 minutes at 50 ° C in the oven.
TBT (max./ret.) = 48 g / g / 35 g / g; AUL = 10.3 g / g; FT: BCD

Example 18

The procedure is as in Example 17, but instead of the Favor® SAB 835 SAB "A" is used.
TBT (max./ret.) = 50 g / g / 36 g / g; AUL = 11.0 g / g; FT: ACD

Example 19

8 g of CMC, Walocel 40000, 2 g of Favor® SAB 835, 0.5 g of BE 600/30 fiber, 0.25 g of TONE 230, 1 g of water and 2 g of i-propanol are homogenized and then brought to 120 ° for 30 minutes C heated in the oven. Thereafter, with 0.6 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and heated to 50 ° C in the oven for 60 minutes.
TBT (max./ret.) = 48 g / g / 32 g / g; AUL = 9.0 g / g; FT: ACD

Example 20

The procedure is as described in Example 19, but who added the only 0.1 g of TONE 230.
TBT (max./ret.) = 45 g / g / 30 g / g; AUL = 8.6 g / g; FT: AD

Example 21

100 g of the product obtained in Example 1 are mixed with 100 ml of a 0.125% aqueous solution of 3,7-bis- (dimethylamino) -phenothiaziniumchlorid mixed and on closing for 2 hours in a convection oven at 60 ° C ge dries.

200 mg of the product thus obtained are placed in a teabag given. This is placed in a beaker containing 50 ml 0.2% Saline hooked. Staining of saline is judged, then the process with new NaCl solution repeated. After one hour, the tea bag is removed.  

Even after the fifth cycle, the blue color shows the cook salt solution the release of the active ingredient from the Spei chermedium acting polymer composition.

Comparative Examples 2-5

The preparation of the products of Examples 1, 3, 11 and 19 were repeated without the addition of TONE 230. The sustain The products were inhomogeneous and could be separated by sieving be and block. Regarding the TBT and the AUL test could because of the inhomogeneity of the products (segregation when screening) no reproducible values are obtained.

Comparative Example 6

20 g of CMC, Walocel 30000 are kept with 8 g of isopropanol, 200 g of water, 0.4 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and 0.8 g of acetic acid at 50 ° C for 4 hours. It is then dried at 80 ° C ge.
TBT (max / ret.) = 16 g / g / 11 g / g; AUL = 8.9 g / g; FT: E

Comparative Examples 7 to 11 (according to Example 1 and 2 of US 4,959,341)

Carboxymethylcellulose (7H, Aqualon), palmitic acid and borate-stabilized dihydroxyaluminum acetate become intimate mixed and then mixed with cellulose fiber. The way obtained materials are ground to about 500 μ.

When trying to sieve the obtained materials, separate these into the components, in particular, the CMC separates from the cellulose fiber. The measurements were therefore unsweetened Used fractions.

Comparative Examples 12, 13

According to Example 6 US 4,959,341 the following solution is prepared:
0.61 g of benzoic acid were dissolved in 7.5 ml of ethanol and mixed with a solution of 1.4 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and 7.5 ml H₂O.

According to Example 7 US 4,959,341, 2 ml each of the solution was mixed with 2.0 g of CMC (7H, Aqualon), 0.4 g of palmitic acid and cellulose fiber (Comparative Example 11 without, Comparative Example 12 with 6.0 g of cellulose fiber).
Results:
without cellulose fiber: TBT (max./ret.): 9/7 AUL: 4.1 Gel thickness (10 Hz): 2650 N / m²
with cellulose fiber: TBT (max / ret.): 10/7 AUL: 5.8 gel strength (10 Hz): not measurable

Comparative Example 14

According to Example 2 US 4,952,550, 20 g of CMC (Aqualon, 7H) were moistened with 8 g of isopropanol. After the alcohol was removed, 200 g of dist. Water, 0.4 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and 0.8 g of glacial acetic acid and heated to 50 ° C for 4 hours. It was then dried for 3 hours in a circulating air dryer.
Result: TBT (max./ret): 15.4 / 9.1 g / g; AUL: 11.4 g / g
In none of the comparative examples was it possible to achieve the level of the absorbers according to the invention with regard to the absorption capacity, in particular under pressure or the level in the gel strength.

For the measurements required for the measurements (cf. Description of the measurement methods) was also a separation of in US 4,959,341 described absorber systems in the used Components observed. This complicates the use of such Systems considerably (separation in the promotion etc.).

Claims (19)

A polymer composition consisting essentially of 70-99.9% by weight of at least one component A based on water-soluble and / or water-swellable polymers based on polysaccharides and derivatives thereof, which have optionally been modified by crosslinking, and
0.1-30% by weight of at least one component B based on water-swellable synthetic polymers and / or copolymers based on (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, Maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and the amides, the N-alkyl derivatives, the N, N'-dialkyl derivatives, the hydroxyl-containing esters and the amino group-containing esters of these polymerizable acids, wherein 2% to 98% of the acid groups of this acid are neutralized,
and wherein these polymers and / or copolymers are crosslinked by at least one at least bifunctional compound, as polymeric components, as well as
0.1-30% by weight, based on these polymeric components, of at least one matrix material having a melting point or softening point below 180 ° C. for preventing segregation and gel blocking,
0.001-10 wt .-%, based on these polymeric components, at least one ionic or covalent crosslinking agent and 0-50 wt .-%, based on the polymeric components, least one antiblocking agent based on natural and / or synthetic fibers and / or Materials with a large surface. 2. Absorbent material composition consisting essentially of
70-99.9 wt .-% of at least one component A based on water-soluble and / or water-swellable polymers based on polysaccharides and derivatives thereof, which may have been modified by crosslinking, and
0.1-30% by weight of at least one component B based on water-swellable synthetic polymers and / or copolymers based on (meth) acrylic acid (meth) acrylonitrile (meth) acrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, male acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and the amides, the N-alkyl derivatives, the NN'-dialkyl derivatives, the hydroxyl-containing esters and the amino include esters of these polymerizable acids where up to 98% of the acid groups of this acid are neutralized,
and wherein these polymers and / or copolymers are crosslinked by at least one bifunctional compound, as polymeric components, as well as
0.1-30% by weight, based on these polymeric components, of at least one matrix material having a melting point or softening point below 180 ° C. for preventing segregation and gel blocking,
0.001-10 wt .-%, based on these polymeric components, at least one ionic or covalent crosslinking agent and 0-50 wt .-%, based on the polymeric components, least one antiblocking agent based on natural and / or synthetic fibers and / or Materials with a large surface. 3. Active substance-containing depot material composition, consisting essentially of 70-99.9 wt .-% of at least one component A based on water-soluble and / or wasserquell ble polymers based on polysaccharides and their Deri derivatives, which may have been modified by crosslinking, and
0.1-30% by weight of at least one component B based on water-swellable synthetic polymers and / or copolymers based on (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, Maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and the amides, the N-alkyl derivatives, the N, N'-dialkyl derivatives, the hydroxyl-containing esters and the amino group-containing esters of these polymerizable acids, wherein 2% to 98% of the acid groups of this acid are neutralized, and wherein these polymers and / or copolymers are crosslinked by at least one at least bifunctional compound, as polymeric components, and 0.1-30 wt. -%, Bezo conditions on these polymeric components, at least one matrix material having a melting point or softening point below half of 180 ° C to prevent segregation and gel blocking, 0.001-10 wt .-%, based at least one antiblocking agent based on natural and / or synthetic fibers and / or materials having a high surface area, based on these polymeric components, at least one ionic or covalent crosslinker and 0-50% by weight, based on these polymeric components this composition releases at least one active substance, for example a medicament, a pesticide, a bactericide and / or a fragrance with a delay. 4. The composition of claim 1, 2 or 3, consisting essentially of
75-90% by weight of component A,
10-25 wt .-% of component B as polymeric components and
2.5-7.5% by weight, based on these components, of at least one matrix material,
3-7 wt .-%, based on these components, of at least one ionic or covalent crosslinker and
0.5-50 wt .-%, preferably 5-15 wt .-% of at least one antiblocking agent. 5. Composition according to one of the preceding claims, since characterized in that component A is a water-soluble and / or water-swellable polymer based on Polysaccha riden and their derivatives, in particular starch, guar and Cellulose derivatives is. 6. Composition according to claim 5, characterized that component A is an anionic derivative of cellulose, before preferably carboxymethylcellulose. 7. Composition according to claims 1 to 4, characterized marked characterized in that the matrix material at room temperature highly viscous or waxy soft consistency. 8. Composition according to claim 7, characterized the matrix material is selected from triglycerol mono stearate, castor oil and / or polycaprolactones, the given if modifi. by reaction with maleic anhydride are graced. 9. Composition according to claims 1 to 4, characterized marked indicates that the ionic crosslinkers are selected Metal compounds, preferably magnesium, calcium, alumi nium, zirconium, iron, titanium and zinc compounds, in Form of their salts with organic and inorganic acids. 10. Composition according to Claims 1 to 4, characterized gekennzeich net, that the covalent crosslinkers are selected from poly functional carboxylic acids, alcohols, amines, epoxy ver  compounds, carboxylic anhydrides and / or aldehydes, as well as their derivatives, as well as their heterofunctional compounds with different functional groups of the above Classes of compounds. 11. A process for preparing the composition according to An Spells 1 to 10, characterized in that the components initially mixed with each other to homogeneity and then the crosslinker terminate through the matrix by means of one the heat treatment is fixed. 12. The method according to claim 11, characterized in that one the components A and B before mixing on a grain size of 90 μm-630 μm. 13. The method according to claims 11 or 12, characterized gekenn characterized in that first mixing the components A and B, the antiblocking agent and the matrix material for this purpose until Homogeneity arises by mixing this at 25 ° C to 180 ° C, preferably 100 ° C to 120 ° C. undergoes a heat treatment, and after the addition of the Ver Netzers this through the matrix at 25 ° C to 180 ° C, before preferably 50 ° C to 80 ° C, fixed. 14. The method according to claims 11 or 12, characterized marked records that all components are physically mixed and then a heat treatment at 25 to 180 ° C, preferably 100 to 120 ° C to pass the crosslinker through the matrix fix. 15. The method according to claims 11 to 14, characterized net, that the components before the final heat treatment with a hydrophilic solvent, preferably in Amounts of 1-10% by weight, based on the polymer mixture, added.   16. The method according to claim 15, characterized in that the solvent is water or a mixture of water with water soluble organic solvents, preferably an alcohol with up to four carbon atoms, more preferably a water / iso propanol mixture, is. 17. A process for the preparation of a Depotmaterialzusammen composition according to claims 10-16, characterized in that the active ingredient

• is absorbed either from aqueous or water-containing solutions of the composition according to claims 1, 2 and 4 to 9 and is optionally dried again,
• - Is added as a solution or dispersion in any precursors of the manufacturing process of said composition.

18. Use of the composition according to claims 1 to 9 or produced according to claims 10 to 16 from fiber, film, Powder or granules for absorption of water-containing Solutions or dispensations, as well as body fluids, in chemical-technical products such as packaging materials, in culture vessels, for soil improvement and as Cable sheath, in hygiene means such as Tampons or diapers or animal hygiene products. 19. Use of the composition according to claims 3 to 9, or prepared according to claim 17, in powder form or as Dispersion in hydrophobic media optionally in combination nation with dispersion stabilizers or in a mixture with other substances.