KR100278391B1 - Polymer compositions, absorbent compositions, methods for their preparation and methods of use - Google Patents

Abstract

The present invention discloses polymer compositions, in particular absorbent compositions or active substance-containing deposits, which are polysaccharide based water-soluble and / or water-expandable polymers, the water-expandable polymers being separated as the main component, as further components used as polymer components. And a matrix material for gel blocking, an ionic or covalent crosslinker, a reactive additive, and also an blocking agent. The present invention also discloses a method for use as a (animal) hygiene article and a chemical technical article containing the polymer composition or absorbent composition, and a method for producing the same.

Description

Polymer compositions, absorbent compositions, methods for their preparation and methods of use

The present invention relates to a polymer composition and an absorbent composition (absorbent material) mainly composed of renewable raw materials. These are in principle biodegradable. Since it is mainly derived from nature, this absorbent, unlike polyacrylate-based absorbents, does not contain residual monomers or contains in very low amounts. The polymer composition and the absorbent composition according to the present invention have a relatively high absorbency and water absorption rate for water and aqueous solution, and have a gel barrier property (gel blocking: the outer layers of the absorbent adhere to each other when contacted with water, so that the liquid no longer enters the absorbent. To prevent them), and they are mechanically stable (in component separation surfaces). When they are in a swollen state, they are separated into individual particles, are insoluble in water, and have very high gel stability. The present invention also relates to a process for preparing the polymer composition, and to water, aqueous or aqueous dispersions and body fluid absorbing fibers, films, powders, or granular materials, sanitary articles such as tampons or diapers, animal hygiene articles, packaging materials (especially , Meats and fish), culture vessels, soil conditioning and cable sheathing methods.

Most of the currently used absorbent materials, also referred to as superabsorbents, are capable of absorbing large amounts of liquid (water, urine) in a short time, and are mainly slightly crosslinked polyacrylates. Therefore, they are not based on renewable raw materials, and their biodegradability is relatively insufficient or not biodegradable at all.

In an effort to make superabsorbents from renewable raw materials, acrylic acid was grafted onto polysaccharides, such as corn starch, as described in DE-C-2612846. However, only a small amount of polysaccharide (less than 25%) can be used, otherwise the absorbency will be greatly degraded.

As described in DE-OS 40 29 591, 40 29 592 and 40 29 593, incorporation of polysaccharides into polymerized gels of polyacrylates can be used to replace polyacrylates, but not The addition of various auxiliaries, such as aluminum cross-linking agents, can replace only up to 25% of the polyacrylates in order not to result in significant degradation of the absorbency and other properties of the resulting superabsorbent. Polysaccharides are considered the basis of absorbents to obtain biodegradable units.

DE-C-3132976 describes the mixing of polyacrylic acid with powdered and solution polysaccharides, wherein the shell of the absorbent particles of the mixture is Al (0H) ₂ OOCCH ₃ * 1 / 3H ₃ BO Crosslink with an aluminum crosslinker such as ₃ . Therefore, this method cannot provide a superabsorbent composed of 60% or more renewable raw materials.

According to the methods disclosed in the art, polysaccharides do not contribute significantly to absorption as an absorbent component.

Various patent publications, such as DE-A-2634539, disclose methods for producing carboxymethylcellulose absorbers, ie, in principle biodegradable materials, by crosslinking carboxymethylcellulose with various crosslinking agents in an aqueous system. have. However, these absorbents exhibit severe gel blocking.

US-A 4 953 341 discloses a process for the preparation of carboxymethyl cellulose-based absorbents using aluminum crosslinkers which cause crosslinking of carboxymethylcellulose during liquid absorption, which absorbs carboxymethylcellulose, cellulose fibers, hydrophobic components. And a mixture of Al (0H) ₂ OOCCH ₃ * 1/3 H ₃ BO ₃ as a cross-linking agent. Although these absorbents have good water absorption, they exhibit a blocking phenomenon. In addition, these absorbents are easily separated by mechanical stress such as sieving or transport and can no longer exist as homogeneous materials, which greatly limits their availability.

EP-B 0 201 895 also discloses a method for producing a carboxymethylcellulose absorbent. However, in the preparation of these absorbents, an aqueous solution in which carboxymethylcellulose is present at low concentration is used. In addition, higher amounts of organic solvents are needed during manufacture. The manufacturing method of the absorbent which has this carboxymethylcellulose as a main component requires very long time. In addition, this absorbent exhibits a blocking phenomenon and low gel strength.

Initially, only very high swelling capacity when the absorbent and liquid contacted, also called free swelling capacity (or swelling capacity), was a major factor in the development of superabsorbents, but after that, not only the amount of liquid absorbed, but also the gel strength. It turns out that it is important. However, the absorbency, also called the swelling or free swelling ability, and the gel strength of the crosslinked polymers exhibit opposite properties as can be seen in US-PS 3,247,171 (Dow / Walker) and US-PS Re 32,649. This means that particularly high absorbing polymers have swelled gels of weak strength, which can deform the gels under applied pressure (eg, body loads), further disrupting liquid distribution and liquid absorption.

According to US-PS Re 32,649, the balance between absorbability (gel volume) and gel strength should be such that when these superabsorbents are used in the manufacture of diapers, they ensure the dryness, liquid absorption and liquid transport of the diaper and skin. do. In this relationship, the ability of the polymer to swell freely first and then to retain the liquid under the pressure applied thereafter is important, as well as the fact that the liquid is absorbed under simultaneous acting pressures, ie during liquid absorption. This is actually important when a baby or person is sitting or lying on hygiene items or when shearing forces are applied, such as the movement of the legs. In EP-A-0 339 461 this specific absorption capacity is referred to as absorption under load ("AUL").

It is an object of the present invention to provide a polymer composition and an absorbent composition (hereinafter referred to as an absorbent) in a simple manner, without the above-mentioned drawbacks and with the following properties (a) to (h).

a) The absorbent consists mainly of components derived from nature and is therefore biodegradable in principle.

b) The absorbent has high mechanical strength and does not separate into individual components during sieving or conveying, for example in a helical screw feeder.

c) The absorbent has a relatively high absorption rate and absorption capacity for water and aqueous solution.

d) The content of residual monomers is much lower than in conventional absorbents based on polyacrylates.

e) The absorbent has very high gel stability under swelling conditions, in which the absorbent particles are present in the form of their respective particles.

f) they do not exhibit gel blocking.

g) The absorbents have high absorption and absorbing capacity under load for water and aqueous solutions.

h) The absorbent is relatively easy to prepare.

According to the present invention, the above object is the following five components, namely

-Component A based on the specific regenerated polysaccharide raw material,

Component B consisting of certain water swellable polymers,

Matrix materials,

Ionic or covalent crosslinking agents, and

-Reactive additives

And an absorbent consisting of a blocking agent optionally added.

Therefore, the present invention

70 to 99.99% by weight of component A, which is mainly composed of a water-soluble and / or water-swellable polymer based on polysaccharides and derivatives thereof optionally modified by ions and / or covalent crosslinking,

(Meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid and / or 2 Water-swellable synthesis based on acrylamido-2-methylpropane sulfonic acid and amides, N-alkyl derivatives, N, N'-dialkyl derivatives, hydroxyl group-containing esters and amino group-containing esters of these polymerizable acids Based on polymers and / or copolymers, 0 to 98% of the acid groups of the acids are neutralized, and the polymers and / or copolymers are crosslinked by at least one compound which is at least difunctional. 0.01 to 30% by weight of component B,

0.1 to 30% by weight of the matrix material for separation and gel barrier prevention, each having a melting point or a softening point of 180 ° C. or less, based on the polymer components A and B,

0.001 to 10% by weight of the ionic and / or covalent crosslinking agent relative to the polymer components A and B,

With respect to the polymer components A and B, 0.1 to 50% by weight of a reactive additive which improves the absorption capacity and / or the absorption rate,

To the polymer components A and B, 0 to 50% by weight of a barrier agent mainly composed of natural and / or synthetic fibers or other representative material

It relates to a polymer composition comprising a.

The present invention also relates to an absorbent composition composed of the above components, and an active material-containing depot material composition of this type, which releases the active material in a delayed form.

Very surprisingly, a slight addition of component B to component A was found to significantly improve absorbency. Since component B only needs to be added in small amounts, the residual monomer content of the absorbent, for example the residual monomer content of acrylic acid, is much lower than the residual monomer content of the polyacrylate-based absorbent.

In addition, by adding a solid material that acts as a matrix of the absorbent system, together with a mixture of components A and B, which are polymer absorbent materials, and an ionic crosslinker, and optionally an antiblocking agent, improved mechanical strength with respect to the separation of the individual dry particles. In addition, it is surprising to find that absorbents having high water absorption and high absorption capacity in water and aqueous solutions can be prepared. In addition, the gel of this absorbent system is present separately in each particle.

Most surprisingly, reactive additives improve absorption, especially under load. It is also surprising that these absorbents (in combination with the above-mentioned properties) have significantly higher gel strengths than absorbers based on polyacrylic acid.

As component A, water-soluble and water-swellable polymers and derivatives thereof based on polysaccharides are suitable, such as guar, carboxymethyl guar, xanthan, alginate, gum arabic, hydroxyethylcellulose or hydroxy. Propyl cellulose, carboxymethylcellulose and other cellulose derivatives, starch and starch derivatives (eg carboxymethyl starch) and mixtures of the respective polysaccharides. Preferred polymers are starch, guar and cellulose, also anionic derivatives thereof, with carboxymethylcellulose being particularly preferred.

The polymers listed as component A can be modified by crosslinking to reduce their solubility in water and to obtain more mixed swelling. Crosslinking may take place on the entire polymer or only on the surface of each polymer particle.

The reaction of the polymer can be carried out using an ionic crosslinker such as calcium, aluminum, zircon, iron (III) compounds. The reaction may also be carried out by polyfunctional carboxylic acids (e.g. citric acid, mucic acid, tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, adipic acid), alcohols (e.g. polyethylene Glycols, glycerol, pentaerythritol, propanediol, saccharose), carbonate esters (e.g. ethylene and propylene carbonate), amines (e.g. polyoxypropylene amine), epoxy compounds (e.g. ethylene Glycol diglycidyl ether, glycol diglycidyl ether or glycol triglycidyl ether and epichlorohydrin), acid anhydrides (eg succinic anhydride and maleic anhydride), aldehydes and polyfunctional (activated) olefins [For example, bis- (acrylamido) -acetic acid and methylene bisacrylamide]. Also suitable are derivatives of the above-described compounds and heterofunctional compounds with different functional groups.

As component B, water-swellable synthetic polymers or copolymers based on (meth) acrylic acid and (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid, maleic anhydride , Itaconic acid, itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid 2-acrylamido-2-methylpropane sulfonic acid and amides, N-alkyl derivatives and N, N'-dialkyl derivatives, hydroxy of these polymerizable acids Water-swellable synthetic polymers or copolymers based on the actual group-containing ester and the amino group-containing ester are suitable. Crosslinked and partially neutralized polyacrylates are preferred.

It is possible to neutralize up to 98%, preferably 50 to 80%, of the acid groups.

The polymers can be crosslinked with at least bifunctional crosslinkers.

The process for preparing the aforementioned polymers can be carried out by known methods (DE-C 27 06 135, DE-0S 40 15 085). Polyacrylates such as FAVOR manufactured by Chemischer Fabric Stockhausen GmbH ) Is a particularly preferred material as component B.

Organic solid materials having a melting point or softening point of 180 ° C. or less and preferably soft consistency at room temperature are suitable as matrices, for example triglycerol monostearate or certain wax esters. Highly viscous liquids such as castor oil are also suitable. Preferably, polycaprolactones such as TONE 0230 and 0240 available from Union Carbide are suitable as matrices, which may be modified, for example, by reaction with maleic anhydride.

The matrix is believed to impart higher mechanical strength to the absorbent system, perhaps by chemical and / or physical interaction, which greatly reduces the component separation that occurs during transport, for example by conveyor screws or by screening. In this way, an absorbent having a high absorbency can be prepared, which is present as a more homogeneous and more effective system even after the final processing or transfer to the desired place.

In addition, by embedding the absorbent in the matrix, the most surprising result is that the gel blocking phenomenon is significantly reduced or even completely eliminated, thereby ensuring a high absorption rate throughout the absorbent. Furthermore, the matrix firmly fixes the crosslinker at the surface of each absorbent particle.

Granulation of the superabsorbent fine powder by the coagulant aid is disclosed in the examples of DE-PS 37 41 157 and DE-PS 39 17 646. The product produced in this way has a high absorption rate in water and aqueous solution. However, since these products consist entirely of polyacrylates, for this reason they are either low or no biodegradable. The flocculant only acts upon the granulation of the product and not as the matrix material.

Blocking agents also reduce gel blocking, so they promote and improve liquid absorption and act to separate the gels, ie, to exist as individual particles. As is generally known, suitable barrier agents include fibrous materials and other surface materials (see DE-C 31 41 098 and DE-C 33 13 344). Representative materials include natural or synthetic fibers, such as wool fibers, cotton fibers, silk fibers and cellulose fibers, or polyamides, polyesters, polyacrylonitriles, polyurethane fibers, olefin fibers and their substitutes and polyvinyl alcohol fibers. And derivatives thereof. Examples of inorganic materials that are surface materials include bentonite, zeolite, aerosil and activated carbon.

Reactive additives, in particular, result in improved absorption and absorption rates under pressure. Suitable reactive additives are substances which increase the concentration of hydrophilic groups in the absorbent and / or cause deformation of the absorbent, increase the fluidity of the gel and / or reduce the electrolyte concentration in the liquid to be absorbed. The reactive additive may be chemically or physically combined with other components. Suitable reactive additives include surfactants, ion exchangers (particularly cation exchangers) or metal salts or complexes which can be hydrolyzed during the preparation of the absorbent, in which the reactive additives can completely or partially replace the blocking agent. . Particularly suitable materials as reactive additives are titanyl sulfates.

Suitable crosslinking agents are compounds which bite the above-mentioned polymers into a state of reduced solubility, improved suction, and reduced blocking.

Metal compounds that can interact with the functional groups of the polymer are suitable ionic crosslinkers. Especially preferred are magnesium, calcium, aluminum, zircon, iron, titanium and zinc compounds which exhibit good solubility in water, such as salts of these metals with carboxylic acids and inorganic acids. Preferred carboxylic acids are acetic acid, lactic acid, salicylic acid, propionic acid, benzoic acid, fatty acids, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, tartaric acid, malic acid and mucous acid. Preferred inorganic anions include chloride, bromide, hydrogen sulfate, sulfate, phosphate, borate, nitrate, hydrogencarbonate and carbonate. Organic compounds containing polyvalent metals such as acetylacetonate (acac) and alcoholates are also suitable, such as Fe (acac) ₃ , Zr (acac) ₄ , Ti (OBu) ₄ and Zr (o-prop) There are _four .

Water-soluble crosslinking agents improve the absorbency by causing the crosslinking of components A and B to each other and to each other, in particular on its surface (DE-PS 31 32 976, DE-0S 26 09 144 and US-A- 4 959 341).

Suitable covalent crosslinkers are polyhydric carboxylic acids, alcohols, amines, epoxy compounds, carboxylic anhydrides and aldehydes and derivatives thereof. Examples include citric acid, slime acid, tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, polyethylene glycol, glycerol, propanediol, polyoxypropylene amine, epichlorohydrin, ethylene glycol diglycidyl ether , Glycol diglycidyl ether, succinic anhydride, maleic anhydride, ethylene carbonate and propylene carbonate. Natural derivatives of the foregoing compounds and heterofunctional compounds with different functional groups are also suitable.

The proportion of component A in the ratio of component A to component B is 70 to 99.99% by weight, preferably 75 to 90% by weight. The fraction of component B is from 0.01 to 30% by weight, preferably from 10 to 25% by weight.

The addition of component B, even in small amounts, results in a significant improvement in absorbency, especially with respect to suction power. Thereby, the absorbency can be surprisingly improved over the pure carboxymethylcellulose material (C.M.C material).

The amount of antiblocking agent is from 0.5 to 50% by weight relative to components A and B, with 5 to 15% by weight being preferred.

The amount of reactive additive is from 0.1 to 50% by weight, preferably from 2 to 10% by weight relative to components A and B.

The amount of crosslinker in the absorbent is from 0.001 to 10% by weight, preferably from 3 to 7% by weight relative to components A and B.

The amount of the matrix material added is 0.1 to 30% by weight, preferably 2.5 to 7.5% by weight relative to components A and B.

The matrix prevents disintegration of the absorbent and also prevents gel blockage, as observed, for example, in pure physical mixtures in US-A 4 952 550.

The preferable manufacturing method of an absorbent is demonstrated below.

To prepare the absorbent according to the invention, component A and component B are physically mixed under dry conditions at room temperature. This material is mixed with the antiblocking agent, the reactive additive and the matrix component until a homogeneous mixture is obtained. Mixing of these components is carried out in a suitable mixer such as a screw mixer, fluid bed mixer, disk mixer or ribbon mixer. The heat treatment is carried out at 25 to 180 ° C, preferably at 100 to 120 ° C. The heating time is 5 to 60 minutes, preferably 20 to 40 minutes. For the heat treatment of the product, conventional dryers, heating furnaces or heating ovens (eg, disk dryers, conveyor dryers, fluidized bed dryers or infrared dryers) are used. Subsequently, aluminum dihydroxyacetate stabilized with an ionic crosslinker, preferably boric acid, is incorporated until a homogeneous mixture is produced at room temperature. To fix the crosslinker to the matrix, the matrix material is melted by heating again at 25 to 180 ° C., preferably 50 to 80 ° C., for 5 to 60 minutes.

The components A and B may be sifted, preferably in the range of 90 to 630 mu m, before mixing.

Although mixing of a matrix component is performed at room temperature, it is also possible to use a matrix component in a melt state. The solubilizer preferably not only thermally deforms component A, i.e. polysaccharides other than polyacrylic acid, but also thermally deforms them and the matrix component and component B of the edge region of component A, preferably in the mixture before heat treatment. Can add a mixture of water / isopropanol. This has a positive effect on the suction of the absorbent. Water and other mixtures of water and water soluble organic solvents may be used in place of the water / isopropanol mixture.

EP-PS 0 083 022 discloses a method of crosslinking an absorbent consisting of polyacrylic acid with a crosslinking agent comprising at least two functional groups and capable of reacting with the carboxyl groups of the polyacrylate. This reaction takes place on the surface of the absorbent particles. DE-PS 33 14 019 and DE-PS 35 23 617 also describe surface crosslinking of polyacrylates by crosslinkers having two or more functional groups. In contrast to the absorbents according to the invention, these patents only describe modifications of polyacrylates, not polysaccharides in the shell, but this never results in sufficient biodegradable absorbents.

Ionic crosslinkers can also be mixed directly in the physical mixture of component A, component B, blocking agents, reactive additives and matrix material, wherein the heating is 5 to 120 to 25 to 180 ° C., preferably 100 to 120 ° C. Minutes, preferably 20 to 60 minutes.

In this process, the aforementioned solvent step can be carried out before or after mixing the crosslinking agent.

The covalent crosslinker may be added to the polymer mixture before or after addition of the matrix as a substitute for the ionic crosslinker or together with the ionic crosslinker. The covalent crosslinker is preferably dissolved in any alcohol / water mixture and added to the polymer mixture under rapid stirring. The amount of solvent is 1 to 10% with respect to the polymer mixture. Then it is heated to 25 to 180 ° C. for 5 to 120 minutes. Water and a mixture of water and a water-soluble organic solvent may be used as the solvent.

The absorbent according to the present invention has good biodegradability compared to a product mainly containing polyacrylic acid, shows a remarkably improved adsorption capacity and suction capacity for a 0.9% solution of sodium chloride in comparison with a known absorbent in a natural state, and has a surprisingly high gel strength. Is very high.

* Products A, B, C, D, F, G: Crosslinked and partially neutralized polyacrylates.

Product E: Crosslinked and partially neutralized polyacrylate-starch-grafted polymer.

Product A: Dry-Star H40, available on Wheels AG

(Dry-Star H40-Huls AG)

Product B: Acualic CA3 available from BASF / Nippon Shokubai

(Aqualic CA3-BASF / Nippon Shokubai)

Product C: Nosolo X50, available from Nosolo

(Norsolor X50-Norsolor)

Product D: Slab 90P, available from Alid Colloid Limited

(Slsorb 90P-Allied Colloids Lted.)

Product E: San Wit IMM5000, available from Guest Celanese

(Sanwet IMM5000-Hoechst Celanese)

Product F: Dow 2000, marketed by Dow Chemical

(Dow 2000-Dow Chemical)

Product G: Acual CAW3, available from BASF / Nippon Shokubai

(Aqualic CAW3-BASF / Nippon Shokubai).

In addition, the mechanical strength (in terms of disintegration into individual components) is greatly improved compared to the above-mentioned absorbents mainly based on renewable raw materials.

The polymer composition according to the invention can be used as an absorbent similar to fibers, films, powders, or granular materials for absorbing aqueous liquids such as water or urine and blood, so diapers, tampons, surgical supplies, cable sheaths, culture vessels It is especially suitable for use in packaging materials for meat, fish or fish and absorbent garments.

In addition, the material is suitable as a storage medium for delayed release of active substances such as pharmaceuticals, insecticides (US 4,818,534; US 4,983,389; US 4,983,390; US 4,985,251) and fragrances, which are degradable. There is an advantage. Therefore, a further advantage lies in the fact that the active substance is completely released.

The active substance containing storage material can be prepared by absorption, preferably by absorbing the concentrated aqueous or hydrous solution into substantially anhydrous absorbent and if necessary drying it again.

The active substance may also be added directly in any preceding step of the preparation process of the absorbent composition or as a solution or dispersion.

The active substance-containing storage material is used in powder form or as a dispersion dispersed in a hydrophobic medium which may consist of a dispersion stabilizer such as an emulsifier or stabilizer, or as a mixture with other substances such as polysaccharides.

For example, these fungicide-containing storage materials can be added to cellulose, guar or starch products or derivatives thereof, such as carboxymethylcellulose, thereby preventing degradation of these materials during prolonged storage and use in aqueous media and thus storage The effect avoids the release of large amounts of active material in the solution.

[Test Methods]

[Tea bag test (TBT)]

A tea bag test was conducted to determine the absorbency. An aqueous 0.9% NaCl solution was used as the test solution.

0.2 g of test substance weighed into a tea bag (selected in the range of 90 to 630 μm sieve) were swollen in the test solution for 10 and 30 minutes respectively. After soaking for 5 minutes (maximum value), it was centrifuged at 1400 rpm in a centrifuge, for example a commercial spin dryer. The liquid absorbance was measured with a gravitational meter and represented in terms of 1 g of substance (holding value).

[Absorption under load (AUL)]

In order to measure the ability of the liquid to absorb under load, the absorbance under load was measured as disclosed in EP-AO 339 461. 0.16 g of test material (selected in the range of 300 to 600 μm in sieve) was swollen by capillary action for 60 minutes under a pressure of 1.55 kN / m 2 (99.8 g./in ² ) in 0.9% NaCl solution. The liquid absorbance was measured by a gravity meter and expressed in terms of 1 g of substance.

[Gel strength (G ')]

In order to measure the gel strength G 'of the swollen absorbent, the method disclosed in EP-A-0 339 461 was used.

Device: Regulated stress flow meter CS 100 (carry-met limited, docked / UK).

Measurement conditions: 60 mm diameter, 2 mm spacing between plates, temperature 20 ° C., torque 1000-4000 μm, amplitude 1.5-5 mrad, frequency 10.0 Hz, plate system of 28 ml of 0.9% NaCl per gram of absorbent. The measured value is expressed in N / m 2.

[Flow test (FT)]

The flow test measured the rate at which the product absorbed the test liquid. In addition, it was examined whether the products exhibited blocking phenomena, whether they were fully swollen, and whether they were totally wetted. Furthermore, it was examined whether the gel was in solid, sticky, or open separated form.

In order to run the flow test, about 100 mg of the material was placed on a cloth soaked in water and water absorption by the product was observed. Absorption properties were evaluated in the following grades:

A: quickly absorbed

B: absorbed very quickly

C: absorbed from beginning to end

D: The gel is present in separate form after water absorption

E: gel blocking.

8 g of CMC, Walocel 40000 (sodium carboxymethylcellulose, product of Wolf Walsrod) was prepared using 2 ml of isopropanol and 1 ml of water and 2 g of Favor (Favor). ) SAB 953 (crosslinked and partially neutralized sodium polyacrylate; product of Stokehausen GmbH), 0.5 g of TONE 230 (caprolactone polyol, molecular weight 1250 g / mol, product of Union Carbide), Mix thoroughly with 0.1 g of tantanyl sulfate and 0.5 g of Al (OH) ₂ OOCCH ₃ * 1 / 3H ₃ BO ₃ and heat to 120 ° C. in an oven for 60 minutes.

TBT (maximum value / retention value) = 51 g / g / 33 g / g; AUL = 15.4 g / g; FT: B C D

Example 2

The same procedure as in Example 1 was followed, but the amount of titanyl sulfate added was increased to 0.25 g.

TBT (maximum value / holding value) = 47 g / g / 29 g / g; AUL = 17.5 g / g; FT: B C D

Example 3

The same procedure as in Example 1 was carried out, but the amount of titanyl sulfate added was increased to 0.5 g.

TBT (maximum value / retention value) = 46 g / g / 28 g / g; AUL = 17.7 g / g; FT: B C D

Example 4

The same procedure as in Example 2 was followed, but 0.5 g of fiber BE 600/30 (cellulose, 17 mm diameter, 30 mm length, product of Rettenmeyer) was further mixed.

TBT (maximum value / holding value) = 48 g / g / 32 g / g; AUL = 17.4 g / g; FT: A C D

Example 5

60 g of C.M.C., Wallace 40 000 were thoroughly mixed with 1.5 g of ethylene carbonate, 1.5 ml of isopropanol and 1.5 ml of water and heated in an oven to 120 ° C. for 1 hour. 8 g of this product is thoroughly mixed with 2 g Faber SAB 953, 0.5 g tow 230, 0.5 g fiber BE 600/30, 0.25 g titanyl sulfate, 1 ml water and 2 ml i-propanol , Heated to 120 ° C. in an oven for 1 hour.

TBT (maximum value / retention value) = 46 g / g / 28 g / g; AUL = 18.2 g / g; FT: B C D

Example 6

The same procedure as in Example 5 was followed, but 1.0 g of fiber was used instead of 0.5 g of fiber.

TBT (maximum value / retention value) = 43 g / g / 26 g / g; AUL = 17.5 g / g; FT: B C

Example 7

The same procedure as in Example 3 was followed, but 0.5 g of fiber BE 600/30 was further used. In addition, 1.0 g of triglycerol monostearate was used instead of the tow 230.

TBT (maximum value / retention value) = 35 g / g / 24 g / g; AUL = 17.8 g / g; FT: C D

Example 8

The same procedure as in Example 4 was followed, but additional 1.0 g of fiber BE 600/30 was added and the mixture was further heated in an oven to 120 ° C. for 1.5 hours instead of 1 hour.

TBT (maximum value / holding value) = 47 g / g / 31 g / g; AUL = 19.0 g / g; FT: A C D

Example 9

100 g of the product obtained in Example 1 were mixed with 100 ml of a 0.125% aqueous solution of 3.7-bis (dimethylamino) -phenothiazinium chloride and dried at 60 ° C. for 2 hours in a recycle air dryer. 200 mg of the product thus obtained was placed in a tea bag. This was suspended in a beaker containing 50 ml of sodium chloride 0.2% solution. After 1 hour, the tea bag was removed. The sodium chloride dye solution was evaluated and the procedure repeated using fresh NaCl solution. Even after five cycles, the sodium chloride solution remains blue to indicate that the active substance is released from the polymer composition serving as the storage medium.

Comparative Example 1

The same procedure as in Example 3 was followed, but 0.5 g of titanium dioxide was used in place of titanyl sulfate.

TBT (maximum value / holding value) = 47 g / g / 32 g / g; AUL = 10.6 g / g; FT: E

Comparative Examples 2 and 3

Tonne 230 was not added and the preparation of the products according to Examples 3 and 5 was repeated. The product was heterogeneous and easily separated. For this reason, reproducible analytical data could not be obtained.

Comparative Example 4

The same procedure as in Example 4 was followed, but no titanyl sulfate was added.

TBT (maximum value / retention value) = 45 g / g / 33 g / g; AUL = 9.9 g / g; FT: A C D

Claims (23)

70-99.99% by weight of component A, which is a water-soluble or water-swellable polysaccharide or polysaccharide derivative, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinylacetate, vinyl pyrrolidone, vinyl pyridine , Maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid or 2-acrylamido-2-methylpropane sulfonic acid and amides, N-alkyl derivatives, N, N'-di of these polymerizable acids Water-swellable synthetic polymers or copolymers based on alkyl derivatives, hydroxyl group-containing esters and amino group-containing esters, wherein from 0 to 98% of the acid groups of the acids are neutralized and the polymer or copolymer is 0.01 to 30% by weight of component B, which is crosslinked by a compound which is at least bifunctional, and a separation and gel difference with respect to the polymer components A and B, each having a melting point or softening point of 180 ° C. or less, respectively. 0.1 to 30% by weight of the matrix material for prevention, 0.001 to 10% by weight of ionic or covalent crosslinking agent relative to the polymer components A and B, and the absorbency or absorption rate of the polymer composition relative to the polymer components A and B 0.1 to 50% by weight of one or more reactive additives to improve the composition, and 0 to 50% by weight of one or more barrier agents, based on natural fibers, synthetic fibers or surface material, based on the polymer components A and B. Polymer composition. The polymer composition of claim 1, which contains at least one active substance selected from medicaments, pesticides, fungicides, or fragrances, wherein the active substance is released in a delayed form. The composition according to claim 1, wherein from 75 to 90% by weight of component A and from 10 to 25% by weight of component B, and from 2.5 to 7.5% by weight of at least one matrix material, are used relative to polymer components A and B. With respect to polymer components A and B, 3 to 7% by weight of one or more crosslinking agents, 2 to 10% by weight of one or more reactive additives with respect to polymer components A and B, and to polymer components A and B, A composition comprising 0.5 to 50% by weight of one or more blocking agents. The composition according to claim 1 or 3, wherein component A is a water-soluble or water-swellable polymer composed mainly of polysaccharides and derivatives thereof. Composition A is characterized in that component A is an anionic derivative of cellulose. The composition of claim 1 or 2, wherein the matrix material is a high viscosity liquid at room temperature or has a waxy soft consistency. 7. The composition of claim 6, wherein the matrix material is selected from the group consisting of triglycerol monostearate, castor oil, wax esters and polycaprolactone, which are optionally modified by reaction with maleic anhydride. The composition of claim 1 or 2, wherein the ionic crosslinker is selected from metal compounds in the form of metal salts with organic and inorganic acids. The method of claim 1 or 2, wherein the covalent crosslinking agent is selected from the group consisting of polyfunctional carboxylic acids, alcohols, amines, epoxy compounds, carboxylic acid anhydrides and aldehydes; Their derivatives; And a heterofunctional compound having two or more functional groups among compounds selected from the group consisting of polyfunctional carboxylic acids, alcohols, amines, epoxy compounds, carboxylic anhydrides and aldehydes. . The composition of claim 1 or 2, wherein the reactive additive is selected from natural surfactants, synthetic surfactants, ion exchangers, or hydrolyzable metal salts or metal salt complexes. The composition of claim 10 wherein the reactive additive is titanyl sulfate. 70-99.99% by weight of component A, which is a water-soluble or water-swellable polysaccharide or polysaccharide derivative, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinylacetate, vinyl pyrrolidone, vinyl pyridine , Maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid or 2-acrylamido-2-methylpropane sulfonic acid and amides, N-alkyl derivatives, N, N'-di of these polymerizable acids Water-swellable synthetic polymers or copolymers based on alkyl derivatives, hydroxyl group-containing esters and amino group-containing esters, wherein from 0 to 98% of the acid groups of the acids are neutralized and the polymer or copolymer is 0.01 to 30% by weight of component B, which is crosslinked by a compound which is at least bifunctional, and a separation and gel difference with respect to the polymer components A and B, each having a melting point or softening point of 180 ° C. or less, respectively. 0.1 to 30% by weight of the matrix material for prevention, 0.001 to 10% by weight of ionic or covalent crosslinking agent relative to the polymer components A and B, and the absorbency or absorption rate of the polymer composition relative to the polymer components A and B 0.1 to 50% by weight of one or more reactive additives to improve the composition, and 0 to 50% by weight of one or more barrier agents, based on natural fibers, synthetic fibers or surface material, based on the polymer components A and B. A process for producing a polymer composition, wherein the components are mixed with each other until uniform, and then the crosslinker is fixed to the matrix by final heat treatment. The process according to claim 12, wherein before mixing the components A and B, the particles are sorted to a particle size of 90 μm to 630 μm. The process according to claim 12 or 13, wherein components A and B are mixed first, and then, antiblocking agents, reactive additives and matrix materials are mixed and heat-treated at 25 ° C to 180 ° C until the mixture is homogeneous, and a crosslinking agent. After addition, it is fixed to the matrix at 25 ℃ to 180 ℃. The method according to claim 12 or 13, wherein the cross-linking agent is fixed to the matrix by physically mixing all the components, followed by heat treatment at 25 ° C to 180 ° C. The method according to claim 12 or 13, wherein a hydrophilic solvent is added to the components before the final heat treatment. The method of claim 16 wherein the solvent is water or a mixture of water and a hydrophilic organic solvent. The method according to claim 12 or 13, wherein the active substance is absorbed into the composition from an aqueous or hydrous solution and optionally dried again; Or a depot material composition, which is added to the composition in a solution or dispersion state at any stage of the composition production method. 70 to 99.99% by weight of component A, which is a water-soluble or water-swellable polysaccharide or polysaccharide derivative, in the form of fibers, films, powders or granular materials for hygiene solutions, dispersions, fluids, urine or blood absorption; (Meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid or 2-acrylic Water-swellable synthetic polymers based on amido-2-methylpropane sulfonic acid and amides, N-alkyl derivatives, N, N'-dialkyl derivatives, hydroxyl group-containing esters and amino group-containing esters of these polymerizable acids, or Copolymer, wherein from 0 to 98% by weight of the acid groups of the acids are neutralized and the polymer or copolymer is crosslinked by a compound having at least a divalent functionality. 0.01 to 30% by weight of component B, 0.1 to 30% by weight of organic matrix material for separation and gel barrier prevention, each having a melting point or softening point of 180 ° C or less, relative to the polymer components A and B, and to the polymer components A and B. , From 0.001 to 10% by weight of ionic or covalent crosslinking agent, from 0.1 to 50% by weight of one or more reactive additives which improves the absorbency or absorption of the polymer composition relative to the polymer components A and B, and the polymer component A And 0 to 50% by weight of one or more barrier agents, based on natural fibers, synthetic fibers or surface material, relative to B. 2. The composition of claim 2 in the form of a dispersion in powder or hydrophobic medium. 70-99.99% by weight of component A, which is a water-soluble or water-swellable polysaccharide or polysaccharide derivative, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinylacetate, vinyl pyrrolidone, vinyl pyridine , Maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid or 2-acrylamido-2-methylpropane sulfonic acid and amides, N-alkyl derivatives, N, N'-di of these polymerizable acids A water-swellable synthetic polymer or copolymer mainly composed of alkyl derivatives, hydroxyl group-containing esters and amino group-containing esters, wherein from 0 to 98% by weight of the acid groups of the acids are neutralized and the polymer or copolymer And gels having 0.01 to 30% by weight of component B, which is cross-linked by a compound which is at least difunctional, and a melting point or a softening point of 180 ° C. or less, respectively, for the polymer components A and B. 0.1-30% by weight of the organic matrix material for blocking protection, 0.001-10% by weight of the ionic or covalent cross-linking agent with respect to the polymer components A and B, and the absorbency of the polymer composition with respect to the polymer components A and B. Or 0.1 to 50% by weight of at least one reactive additive which improves the absorption rate, and 0 to 50% by weight of at least one barrier agent mainly composed of natural fibers, synthetic fibers or surface material with respect to the polymer components A and B. A chemical technical article containing a polymer composition comprising. The composition of claim 1 wherein component A is crosslinked. 20. The hygiene article of claim 19 which is a tampon, diaper or hygiene article for animals.