DE4206850C2 - Polymer compositions, preparation of polymer compositions, in particular absorption materials and their use - Google Patents

Description

The invention relates to polymeric material compositions as well the preparation of a polymer composition and in particular Absorbent materials that are predominantly renewable Based on raw materials and thus basically biologically are degradable. Due to the predominantly native origin ent the absorbers do not or significantly lower quantities Residual monomers as polyacrylate-based absorbers. The inventor Absorbers according to the invention have a comparatively high density capacity and speed, even under pressure Water and aqueous solutions show no tendency to gel blocking (Gelblocking: When in contact with water stick the outer layers of the absorber and prevent another Penetration of the liquid into the absorber) and are mecha stable (with regard to separation into the individual compo components). In the swollen state they separate into individual Particles, they are not watery and have a very high level Gel stability on. The invention further relates to their Ver for the absorption of water, aqueous solutions and Kör perfluids in hygiene and animal hygiene articles, in Ver Packing materials for meat and fish, in culture dishes as well as for soil improvement 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 at all biolo gable degradable.  

In an effort to produce superabsorbents from renewable raw materials was constructed as described in DE-PS 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 40 29 591, 40 29 592 and 40 29 593, the Po lyacrylates only up to max. 25% will be replaced without one significant deterioration in capacity and others To obtain properties of the resulting superabsorbent although in addition various adjuvants such as fibers and z. B. Aluminum crosslinkers are added. The polysaccharides who as seen as building blocks for the absorber to biodegrade to obtain buildable units.

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 aluminum crosslinking such as Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ is crosslinked. Accordingly, even with this method no superabsorbent can be represented, which consist of over 60% renewable resources.

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

Numerous publications such as DE-OS 26 34 539 beschrei the production of carboxymethylcellulose absorbers, So of materials that are biodegradable in principle are, by a crosslinking of the carboxymethyl cellulose with various crosslinkers in the aqueous system. These absorbers show however, a strong gel blocking.

In the US-A 4,959,341 the preparation of a carboxymethylcellulose based absorber is described which consists of a mixture of carboxymethylcellulose, cellulose fibers, a hydrophobic component and Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ as a crosslinker, the aluminum crosslinker a Crosslinking of the carboxymethylcellulose during the liquid absorption causes.

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-PS 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 only in low concentration  is present. Furthermore, in the production of larger quantities on organic solvents such as acetone, methanol, etc. Be forces. The preparation of these carboxymethylcellulose Absor ber also requires a lot of time. The absorber even show block phenomena and a low gel strength.

While in the development of the superabsorbent initially alone the very high swelling capacity when in contact with liquid, too Free source capacity called, stood in the foreground, has become later shown that it is not only on the amount of absor Baked liquid arrives, but also on the gel solid ness. Absorptive capacity or swelling capacity or free Swelling capacity called on the one hand and gel strength in one cross-linked polymer on the other hand, however, presented contradictory Properties, as already known from US-A 3,247,171 (DOW / WALKER) is known, also from the US-PS Re 32, 649th This means that polymers with particularly high absorption only a low strength of the swollen gel with the result that the gel is applied under one Pressure (eg body pressure) is deformable and the further Liquid distribution and absorption prevented. After US-PS Re 32,649 should therefore have a balance between absorption capacity (gel volume) and gel strength aspires to be so when using such super absorber in a diaper construction fluid intake, Fluid transport, dryness of the diaper and the skin are guaranteed. It is not just important that the polymer liquid under the subsequent action of a Pressure can restrain after the polymer swell freely could, but also, liquids against  a simultaneous, d. H. while the liquid absorbs tion to exert exerted pressure, as under practical Realities happen when a baby or a person is up a sanitary article sits or lies or if it, z. B. by leg movement, to the development of shear forces comes. The specific absorption characteristic is found in the EP-A-0 339 461 on page 5 to 7 as recording under pressure ("Absorption Under Load" = "AUL").

The present invention was based on the object, a Polymer composition, in particular an absorber, ready to produce and manufacture the men described above gel does not have and the following properties be sitting:

• a) The absorber is predominantly made of components native Origin and therefore also biologically be degradable.
• b) The absorbers should have a high mechanical strength have, they may sieve or z. B. at a Screw conveyance not in their individual components separate.
• c) The absorbers should be comparatively high Recording speed and capacity for water and have aqueous 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.
• g) The absorbers should have a high recording speed and Absorption capacity under pressure for water and aqueous Own solutions.

Another task is to provide a drug-containing composition, their preparation and Use.

According to the solution of the first task by a polymer composition and a manufacturing method for a polymer composition, in particular a Absorbent, the (essentially) of four Components consists of:

• - a component A, which is based on renewable special Based on raw materials,
• - a component B, which consists of a special water-swellable polymers,
• a matrix material,
• an ionic or covalent crosslinker,
• - And optionally an antiblocking agent.

The present invention relates to a Polymerzusammenset tion, in particular Absorbtionsmaterialzusammensetzung, consisting essentially of
70-99.99 wt .-% of a component A based on wasserlös Licher and / or water-swellable polymers based on polysaccharides, and derivatives thereof, which may have been modified by crosslinking, and
0.01-30% 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 (- anhydride), 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, hy hydroxyl-containing esters and amino-containing esters of these polymerizable acids , in which
0-98% of the acid groups of these acids are neutralized, and wherein these polymers and / or copolymers are crosslinked by a min-bifunctional compound, as polymeric components, as well as 0.1-30 wt .-%, based on these polyme ren components, a 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, of an ionic or covalent crosslinker, and optionally 0-50 wt .-%, based on these polymeric components, of at least one antiblocking agent based on natural and / or synthetic fibers and synthetic fibers / or high surface area materials obtainable by combining component B with component A in an aqueous medium and then drying and milling,
adding the further components, mixing to homogeneity and carrying out a heat treatment and optionally fixing the crosslinker after this heat treatment with the matrix by a final heat treatment.

The present invention thus further relates to Process for the preparation of a polymer composition, in particular an absorber material, essentially consisting of 70-99.99 wt .-% of a component A based water-soluble and / or water-swellable polymers based on of polysaccharides and their derivatives, optionally have been modified by cross-linking and 0.01-30% by weight 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 (anhydride), 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, hydroxyl-containing esters and amino group-containing esters of these polymerizable acids, wherein 0-98% of Acid groups of these acids are neutralized, and wherein these polymers and / or copolymers by an at least bifunctional compound are crosslinked as polymeric Components, and 0.1-30 wt .-%, based on these polymeric components, a matrix material having a Melting point or softening point below 180 ° C for Prevention of segregation and gel blocking, 0.001-10 Wt .-%, based on these polymeric components, one ionic or covalent crosslinker, and optionally 0-50% by weight, based on these polymeric components, at least one Antiblocking agent based on natural and / or  synthetic fibers and / or materials with large Surface, characterized in that one receives this (s), by mixing the component B with the component A in aqueous Bringing medium together and then drying and grinding, Add the other components, to homogeneity mixes and performs a heat treatment and optionally upon addition of the crosslinker after this heat treatment, this with the matrix through a final heat treatment fixed.

It was surprisingly found that in the Her a minor addition to component B Component A shows a marked improvement in the absorption level effects. Since only minor additions to component B are necessary, so that the residual monomer content of z. B. Acrylic acid of such an absorber significantly lower than in Polyacrylate-based absorbers.

The incorporation of component B into component A becomes for example, by jointly swelling this in water or an aqueous solution and then drying it enough. Surprisingly, this process leads to a significant increase in the AUL value; besides, over surprisingly, the proportion of component B is significantly reduced without the absorption properties of the Pro affected.

Furthermore, it was surprisingly found that by the Addition of a solid as a matrix for the absorber system, in combination with the polymer absorption medium, a mixture of components A and B, and one ionic crosslinker, an absorbent can be produced, the high recording speed and capacity for Water and aqueous solutions as well as an improved mecha niche strength in terms of segregation of  has single dry particles. Continue to lie the Gels of this absorber system separated into individual particles in front.

In addition, these absorbers surprisingly, in addition to the above properties, a gel strength, the German higher than that of absorbers based on polyacrylic build up acid base.

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 Guar and the anionic derivatives of starch, guar and Cel cellulose, with carboxymethyl cellulose being a particularly preferred represents the 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 is poly functional carboxylic acids such as citric acid, mucic acid, Tartaric acid, malic acid, malonic acid, succinic acid, glutar acid, adipic acid, with alcohols such as polyethylene glycols, Glycerol, pentaerythritol, propanediols, sucrose, with Koh acid esters such as ethylene and propylene carbonate, with amines such as polyoxypropylene amines, with epoxy compounds such as ethylene glycoldiglydcidyl ether, glycol di- or triglycidyl ether and Epichlorohydrin, with acid anhydrides such as succinic anhydride and maleic anhydride, with aldehydes and polyfunctional nelle (activated) olefins such as bis (acrylamido) acetic acid and methylenebisacrylamide possible. Likewise, of course, come Derivatives of the mentioned classes of compounds into consideration as well heterofunctional compounds with different functionalities len groups of the above 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, Itaconic anhydride, fumaric acid, vinylsulfonic acid, 2-acrylic amido-2-methylpropanesulfonic acid, as well as the amides, their N and N, N'-dialkyl derivatives, hydroxyl-containing esters and amino Group-containing esters of polymerizable acids suitable net. Preference is given to crosslinked, partially neutralized poly acrylates.  

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 method (DE-PS 27 06 135, DE-OS 40 15 085). On particularly preferred material as component B are poly acrylates, e.g. B. from the chemical factory Stockhausen GmbH produced FAVOR® types.

Components A and B may be chemically, i. H. about ester or by one of the listed crosslinkers or physically, d. H. in the sense of an "Interpenetrating Network" (IPN).

As a matrix organic solids are suitable, which are under 180 ° C melt or soften and preferably in space temperature have a soft consistency, such. B. Trigly cerinmonostearat. Likewise, highly viscous liquids are like z. 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 anhydride.

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 a packaging or after incorporation in his Ver application as a more homogeneous and thus more efficient 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 Agglo merierungshilfsmittel is used in the examples of DE-PS 37 41 157 and DE-PS 39 17 646 described. The so forth put products have a high recording speed for water and aqueous solutions. These products exist however, only polyacrylates and are therefore comparative inadequate or not at all biodegradable. The agglomerating agents are only for granulation of a Product and not as 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 other materials with 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 water solubility, as 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 inorgan Anions are chlorides, bromides, hydrogen sulfates, Sul fate, phosphates, borates, nitrates, bicarbonates and car carbonates.

Furthermore, organic compounds are suitable, the more containing valuable metals, such as acetylacetonates and alcohols late, such as 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-PS 31 32 976, DE-PS 26 09 144 and US-A 4,959,341 beschrie ben, the absorption properties are improved.

As covalent crosslinkers are polyfunctional carboxylic acids, Alcohols, amines, epoxy compounds, carboxylic anhydrides and Aldehydes, and their derivatives suitable. Examples are Ci tronic acid, mucic acid, tartaric acid, malic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, polyethylene glycols, Glycerine, propanediols, polyoxypropyleneamines, epichlorohydrin, Ethylene glycol diglycidyl ether, glycol diglycidyl ether, Bern Steinsäureanhydrid, maleic anhydride, ethylene carbonate and Propylene carbonate.

Likewise, natural derivatives of said compound come considered and heterofunctional compounds with various functional groups of the above-mentioned Ver classes of compounds.

The proportion of component A to the ratio of component A to Component B is 70 to 99.99% by weight, preferably 75 to 95% by weight. The proportion of component B is from 0.01 to 30 Wt .-%, preferably 5-25 wt .-%.  

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 necessary proportion of component B is replaced by a Processing of components A and B, for example in ge swollen state and subsequent drying still clear reduced.

The amount of anti-blocking agent is preferably between 0.5 and 50 wt .-%, more preferably 5 to 15 Wt .-% based on the 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 material prevents the Ab from falling apart sorption material, as in pure physical Mischun conditions such as For example, US-A-4,952,550 is observed and prevented additionally a gel blocking.  

The preferred preparation of the absorbent material is described below.

Stage 1) The component A and the component B are physi kalisch mixed in dry form at room temperature. Then this is allowed to stir in water, or in an aqueous Dissolve solution together. After 15 to 360 minutes that will be Material obtained at 40 ° C to 180 ° C in a drying oven ge dries. The product obtained is then ground.

Stage 2) The resulting material is treated with the anti-blocking agent Medium and the matrix component mixed until a homogeneous Mixture is present. The mixing of the components takes place in suitable mixers such as screw mixers, fluidized bed bed mixers, disc mixers or ribbon blenders.

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

Step 3) Subsequently, the ionic crosslinker, preferably aluminum dihydroxyacetate stabilized with boric acid, vigorously ge at room temperature with the material obtained mixes until a homogeneous mixture has formed. to Fixation of the crosslinker through the matrix is repeated 25 ° C to 180 ° C, preferably at 50 ° C to 80 ° C, for 5 to 60 Heated minutes to melt the matrix material.  

Optionally, instead of the one described in Step 1 Processing, component A into (eg with water) swollen component B or component B into the (eg. with water) swollen component A or (eg. with water) swollen component A into (eg with Water) swollen component B, optionally with the addition of Water or an aqueous solution are incorporated.

After grinding (step 1), the product can be screened off, preferably to a particle size 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 in stage 2 may be before the thermal modification with a preferably water / Isopropanol mixture are added to a Lösungsvermit to have a job. Instead of the water / isopropanol mixture can also water and other mixtures of water with water-soluble chen 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 be also write the surface crosslinking of Polyacry laten with the help of crosslinkers, the at least two funktio own groups. In contrast to the invention Absorbers in these patents are only modifications of Polyacrylates, but not of polysaccharides, in the shell described, but by no means obtained absorbers who those that are sufficiently biodegradable.  

The incorporation of the ionic crosslinker can also be directly in the physical mixture of stage 2), then what at 25 ° C to 180 ° C, preferably at 100 ° C to 120 ° C, for 5 heated to 120 minutes, preferably for 20 to 60 minutes becomes.

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 ° C to 180 ° C for 5 to 120 minutes heated. As a solvent, water and mixtures of Water with water-soluble organic solvents ver be used.

Optionally, the antiblocking agents as well as the covalent crosslinkers are already added in stage 1).

The absorbent material according to the invention shows a good bio logical degradability to products on a Po lyacrylsäurebasis, 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, even under pressure, at a surprisingly high 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 1  10000 Superabsorber from example 3  10000 Superabsorber from Ex. 5  10000 Superabsorber from Ex. 7  10000 Superabsorber from Ex. 9  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 (with respect to Ent mixture 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 absorption material as fiber, film, powder or Granules are used to make water or aqueous liquids such as urine and blood, and is especially for use in diapers, tampons, surgical products, cable sheathing, culture containers, packaging materials for meat or fish and suitable for absorbent garments.

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 Storage medium is degradable.

This results in a further advantage that the active ingredient completely released.

The active substance-containing depot materials can by Absorp tion, preferably concentrated, aqueous or water containing solutions in the largely dry absorber and if necessary, its renewed drying can be produced.

The active ingredient may also be used directly or as a solution or dis persion at any precursors of the manufacturing process be added to the absorber composition.  

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 bactericidal tiger depot materials to cellulose, guar or starch products or their derivatives, such as carboxymethylcellulose, when stored and used in aqueous media of the Preventing degradation of these substances for a long time and wherein the depot effect larger amounts of free action substance 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 drop (maximum) was in a centrifuge, such. In a commercial Wäscheschleuder, abge at 1400 rpm flings. The fluid intake became gravimetric determined and converted to 1 g of substance. (Retention value).  

Absorption under load (AUL)

To determine the liquid absorption capacity under pressure, was the absorption under load, as in EP-A 0 339 461 be 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 kN / 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, plat pitch 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 were placed on a paper towel soaked with water and ver, as the water was absorbed by the products. The absorption behavior was evaluated according to the following grading scale.
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

The invention is characterized by manufacturing and Application examples explained in more detail.

precursors

The following mixtures are used at room temperature peratur (15 to 20 ° C) stirred into 360 ml of water and three Hours left. Thereafter, the obtained gels dried for two hours at 100 ° C in a convection oven, then ground and ground to a grain size of Sieved 90-630 μm.

Precursor 1

38 g of CMC Walocel 40000 (sodium carboxymethylcellulose, Wolff Walsrode), 2 g of a polyacrylate superabsorbent (prepared according to DE-OS 40 15 085, Example 4, hereinafter "SAB A" called).  

Preproduct 2

38 g CMC, (Walocel 30000), 2 g "SAB A"

Preproduct 3

36 g CMC, (Walocel 30000), 4 g "SAB A"

Precursor 4

32 g CMC, (Walocel 30000), 8 g "SAB A"

Precursor 5

32 g CMC, (Walocel 30000), 8 g "SAB A", 4 g cellulose fiber (PWC 500, company Rettenmaier)

Precursor 6

28.5 g CMC, (Walocel 30000), 9.5 g guar gum (type 104, Fa. Roeper), 2 g "SAB A"

Precursor 7 (comparative product)

40 g CMC, (Walocel 40000) without additive  

example 1

5 g of the precursor 1 are with 0.25 g (cellulose, diameter: 17 microns, length: 30 microns) fiber BE 600/30 (Rettenmaier) and 0.25 g acid-terminated TONE 230 (a reaction product of TONE 230 polyol on the basis of prolacton, molecular weight 1250 g · mol ^-1 ) from. Union Carbide and maleic anhydride) vigorously mixed and then heated for 30 minutes at 120 ° C in the oven. Then with 0.25 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and heated for one hour at 50 ° C in the oven.
TBT (max./ret.) = 48 g / g / 26 g / g; AUL = 18.0 g / g; FT: BCD

Example 2

5 g of the precursor 2 are vigorously mixed with 0.25 g of Aerosil R 972 (pyrogenic silica, particle diameter: 16 nm Degussa AG), 0.25 g of acid-terminated TONE 230, 0.5 ml of water and 1 ml of i-propanol and then heated for 30 minutes at 120 ° C in the oven. Then with 0.25 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ and heated for one hour at 50 ° C in the oven.
TBT (max./ret.) 51 g / g / 28 g / g; AUL = 19.6 g / g; FT: BCD

Example 3

The procedure is as in Example 2, but instead of the precursor 2, the precursor 3 is used; In addition, Aerosil A 200 (pyrogenic silica, particle diameter: 12 nm Degussa AG) is used instead of Aerosils R 972.
TBT (max./ret.) = 45 g / g / 27 g / g; AUL = 17.0 g / g; FT: BCD

Example 4

The procedure is as in Example 2, but instead of the acid-terminated TONE 230 pure TONE 230 is used; except that is vigorously mixed with twice the amount of water and twice the amount of i-propanol.
TBT (max./ret.) = 52 g / g / 29 g / g; AUL = 19.0 g / g; FT: BCD

Example 5

The procedure is as in Example 2, but the pre-product 5 is used.
TBT (max / ret.) = 47 g / g / 27 g / g; AUL = 18.3 g / g; FT: BCD

Example 6

The procedure is as in Example 3, but only half the amount of acid-terminated TONE 230 is used, except that the Aerosil A 200 is replaced by the same amount of fiber BE 600/30.
TBT (max./ret.) = 52 g / g / 29 g / g; AUL = 18.7 g / g; FT: BCD

Example 7

The procedure is as in Example 2, but in addition (before the first heating) 0.25 g of fiber BE 600/30 tet processing.
TBT (max./ret.) = 49 g / g / 28 g / g; AUL = 18.9 g / g; FT: BCD

Example 8

The procedure is as in Example 2, but the Vorpro product 6 is used.
TBT (max / ret.) = 38 g / g / 22 g / g; AUL = 16.5 g / g; FT: ACD

Example 9

The procedure is as in Example 2, but the Vorpro product 5 is used. In addition, the amount of Aluminiumver network is reduced to 0.2 g.
TBT (max./ret.) = 49 g / g / 28 g / g; AUL = 16.8 g / g; FT: ACD

Example 10

100 g of the product obtained in Example 1 are mixed with 100 ml of a 0.125% aqueous solution of 3,7-bis (dimethyl amino) -phenothiaziniumchlorid mixed and then for 2 h in a convection oven at 60 ° C dried.  

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. After an hour, the tea will be removed. The color of the saline solution will beur shares, then the process with new NaCl solution again get.

Even after the 5th cycle shows the blue color of the common salt Solve the release of the drug from the store medium acting polymer composition.

Example 11

In the preparation of precursor 1, an additional 0.05 g 3,7-bis (dimethylamino) -phenothiazinium chloride to the Pul given mixture and further processed as described. For this precursor according to Example 1 is an absorber ago posed. The absorber thus shown becomes as in Example 10 described examined. The results obtained are correct with those obtained in Example 10 coincide.

Comparative Examples Comparative Example 1

The procedure is as in Example 2, but the Vorpro product 7 is used and halved the amount of acid-terminated TONE 230.
TBT (max./ret.) = 36 g / g / 27 g / g; AUL = 8.0 g / g; FT: E

Comparative Example 2

20 g of CMC 30000 are maintained 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.degree.
TBT (max / ret.) = 16 g / g / 11 g / g; AUL = 8.9 g / g; FT: E

Comparative Examples 3, 4

The preparation of the products of Examples 3 and 5 wur repeated without the addition of a matrix material. The obtained products were inhomogeneous, could by sieving be disconnected and blocked. Regarding the TBT and the AUL Due to the inhomogeneity of the products (Ent mixture when screening) no reproducible values become.

Comparative Example 5

60 g of CMC 40000 are vigorously mixed 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 (crosslinked, partially neutralized polyacrylate from Stockhausen GmbH), 0.5 g of TONE 230, 0.5 g of BE 600/30 fiber and 0.5 g of Al (OH) ₂OOCCH₃ _* 1/3 H₃BO₃ vigorously mixed ver using 2 ml of isopropanol and 1 ml of water 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

Comparative Examples 6 to 10 (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 11, 12

According to Example 6 US 49 59 341 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 49 59 341, 2 ml each of the solution were mixed with 2.0 g CMC (7H, Aqualon), 0.4 g palmitic acid and cellulose fiber (Comparative Example 11 without, Comparative Example 12 with 6.0 g 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 13

According to Example 2 US 49 52 550, 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 could the level of Absorber according to the invention with respect to Absorption capacity, especially under pressure or the level in the gel strength can be achieved.

For the measurements required for the measurements (cf. Description of the measurement methods) was also a separation of in US 49 59 341 described absorber systems in the used Components observed. This complicates the use of such Systems considerably (separation in the promotion etc.).

Claims (28)

1. Polymer composition, in particular Absorbsorptionsmate rialzusammensetzung, consisting essentially of 70-99.99 % By weight of a component A based on water-soluble and / or water-swellable polymers based on polysaccharides and their derivatives, which may be modified by cross-linking and 0.01-30% by weight of a component B, based on water-swellable synthetic polymers and / or Copolymers based on (meth) acrylic acid, (meth) acrylni tril, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid (anhydride), itaconic acid (anhydride), Fu marsäure, vinylsulfonic acid and / or 2-acrylamido-2-methylpro pansulfonic acid and the amides, the N-alkyl derivatives, the N, N'-dialkyl derivatives, hydroxyl-containing esters and ami nogruppenhaltigen esters of these polymerizable acids, wherein 0-98% of the acid groups of this acid neutralized are, and wherein these polymers and / or copolymers by a at least bifunctional compound are crosslinked, as po Polymer components, and 0.1-30 wt .-%, based on these polymeric components, a matrix material having a Melting point or softening point below 180 ° C for Prevention of segregation and gel blocking, 0.001-10 wt .-%, based on these two polymeric Kompo nenten, an ionic and / or covalent crosslinker, and 0- 50 wt .-%, based on these polymeric components, little of an antiblocking agent based on natural and / or or synthetic fibers and / or materials with large Surface, available  by mixing the component B with the component A in aqueous Bringing medium together, then drying and grinding, the added to other components, mixed until homogeneous and performs a heat treatment and optionally at Add the crosslinker after this heat treatment this through the matrix through a final heat treatment fixed. 2. Active ingredient-containing composition, essentially consisting of a composition according to claim 1 and at least one active substance, for example a medicament tel, a pesticide, a bactericide and / or an odor substance released with a delay. 3. Composition according to claim 1 or 2, essentially consisting of 75-95% by weight of component A, 5-25% by weight Component B, as polymeric components and 2.5-7.5 wt%, based on these components, at least one matrixmate Rials, 3-7 wt .-%, based on these components, little at least one ionic and / or covalent crosslinker and 0.5- 50 wt .-%, preferably 5-15 wt .-%, based on these Components of at least one antiblocking agent. 4. Composition according to claims 1, 2 or 3, characterized ge indicates that component A is a water-soluble and / or water-swellable polymer based on Polysaccharides and their derivatives, especially guar, Starch and cellulose derivatives is. 5. Composition according to claim 4, characterized that component A is an anionic derivative of cellulose,  in particular of carboxymethylcellulose. 6. Composition according to claims 1, 2 or 3, characterized ge indicates that the matrix material is a substance that is highly viscous at room temperature or a waxy soft consistency. 7. Composition according to claim 6, characterized the matrix material is selected from triglycerol mono stearate, castor oil and polycaprolactones, optionally modified by a reaction with maleic anhydride are. 8. Composition according to claims 1, 2 or 3, characterized characterized in that the ionic crosslinkers are selected of metal compounds, preferably magnesium, calcium, Aluminum, zirconium, iron, titanium and zinc compounds in the form of their salts with organic and inorganic acids. 9. Composition according to claims 1, 2 or 3, characterized ge indicates that the covalent crosslinkers are selected from polyfunctional carboxylic acids, alcohols, amines, epoxies compounds, carboxylic acid anhydrides and / or aldehydes, as well as their derivatives and heterofunctional compounds with ver different functional groups of said compound classes.   10. Process for the preparation of a polymer composition, in particular an absorber material, essentially be consisting of 70-99.99 wt .-% of a component A based water-soluble and / or water-swellable polymers based on of polysaccharides and their derivatives, optionally have been modified by cross-linking and 0.01-30% by weight a component B, based on water-swellable synthetic Polymers and / or copolymers based on (meth) acrylic acid, (Meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinylpyridine, maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinylsulfonic acid and / or 2-acrylic amido-2-methylpropanesulfonic acid and the amides, the N-alkyl derivatives which contain N, N'-dialkyl derivatives, hydroxyl-containing Esters and amino-containing esters of these polymerizations capable acid, with 0-98% of the acid groups of this acid are neutralized, and wherein these polymers and / or Copo lymere by an at least bifunctional compound ver are, as polymeric components, and 0.1-30 wt .-%, based on these polymeric components, a matrixmate Rials with a melting point or softening point below of 180 ° C to prevent segregation and gel blocking, 0.001-10 wt .-%, based on these two poly meren components, an ionic and / or covalent Ver netzers, and 0-50 wt .-%, based on this polymeric Kom components, based on at least one antiblocking agent natural and / or synthetic fibers and / or materials alien with a large surface, characterized in that one this is obtained by mixing component B with the compo component A in an aqueous medium, then Dries and grinds, mixes the other ingredients until mixes to homogeneity and performs a heat treatment and optionally when the crosslinker is added after this heat Treat this through the matrix with a final one  Heat treatment fixed. 11. The method according to claim 10, characterized in that a polymer composition, in particular an absorber material consisting essentially of 75-95% by weight of com Component A, 5-25% by weight of component B, as a polymeric compo nenten and 2.5-7.5 wt .-%, based on these components, at least one matrix material, 3-7 wt .-%, based on these components, at least one ionic and / or kova lenten crosslinker and 0.5-50 wt .-%, preferably 5-15 Wt .-%, based on these components, at least one anti blocking agent. 12. The method according to claims 10 or 11, characterized gekenn records that as component A is a water-soluble and / or water-swellable polymer based on Polysaccharides and their derivatives, especially guar, Starch and cellulose derivatives used. 13. The method according to claim 12, characterized in that as component A, an anionic derivative of cellulose, in particular of carboxymethyl cellulose. 14. The method according to claims 10 or 11, characterized marked draws that a substance is used as the matrix material, which is highly viscous at room temperature or a wax having a similar soft consistency. 15. The method according to claim 14, characterized in that the matrix material is selected from triglycerol monostearate, Castor oil and polycaprolactones, optionally through a reaction with maleic anhydride are modified. 16. The method according to claims 10 or 11, characterized marked indicates that the ionic crosslinkers are selected  Metal compounds, preferably magnesium, calcium, aluminum minium, zirconium, iron, titanium and zinc compounds in Form of their salts with organic and inorganic acids. 17. The method according to claims 10 or 11, characterized marked indicates that the covalent crosslinkers are selected polyfunctional carboxylic acids, alcohols, amines, epoxies compounds, carboxylic anhydrides and / or aldehydes and their derivatives and heterofunctional compounds with ver various functional groups of said connection classes. 18. The method according to claims 10 to 17, characterized marked characterized in that the component B in the manner with Kompo contacted by contacting both components, bringing them together in aqueous medium, then in a what the solution or dispersion that swells, dries and grinds. 19. The method according to claim 18, characterized in that Either both polymeric components in a dry form mixes or a dry polymeric component with the other polymeric component in already one by a wasserent holding solution or dispersion swollen form ver mixed. 20. The method according to claims 10 to 17, characterized marked characterized in that the component B in the manner with the Component A is contacted by passing through a water holding solution or dispersion swollen component B with a water-containing solution or dispersion swollen component A optionally with the addition of a water-containing solution or dispersion, the compo  nents dries and grinds. 21. The method according to any one of the preceding claims, characterized characterized in that the bringing together of the polymer components and the mixing of the other components Temperatures from 0 ° C to 100 ° C, preferably at room temperature takes place. 22. The method according to claims 18 to 21, characterized marked characterized in that the drying is carried out at 40 ° C to 180 ° C. and the milled product to a grain size of 90 to 630 microns is screened. 23. The method according to any one of the preceding claims, characterized in that the heat treatment at 25 ° C. to 180 ° C, preferably 100 ° C to 120 ° C and the final Heat treatment at 25 ° C to 180 ° C, preferably 50 ° C to 80 ° C is performed. 24. The method according to any one of the preceding claims, characterized, may be following the grinding the other components in the presence of a wasserent holding solution or dispersion, preferably water or a mixture of water and a water-containing organic solvent, admixed. 25. The method according to any one of the preceding claims, characterized in that the crosslinker in a Mixture of water and / or a hydrous organic Solvent dissolves or disperses and the one to be contacted Polymer components or the other components before  Heat treatment supplies. 26. A process for the preparation of a depot material composition according to claims 10 to 25, characterized in that the active ingredient

• is absorbed either from aqueous or water-containing solutions of the composition according to claims 1 and 3 to 9 and is optionally dried again,
• or added as a solution or dispersion to any precursors of the manufacturing process of said composition.

27. Use of the composition according to claims 1 and 3 to 9 or produced according to claims 10 to 25 as fiber, Film, powder or granules for the absorption of water-containing solutions or dispersions and (body-) Liquids in chemical-technical products such as For example, in packaging materials, in culture vessels, for soil improvement and as a cable sheath or in Hygiene articles such as tampons or Windein and Animal hygiene articles. 28. Use of the composition according to claims 2 to 9 or prepared according to claim 26, in powder form or as Dispersion in hydrophobic media optionally in Combination with dispersion stabilizers or in mixture with other substances.