EP1341958A1

EP1341958A1 - Textile material finished with polymeric cyclodextrins, and method for the production thereof

Info

Publication number: EP1341958A1
Application number: EP01989583A
Authority: EP
Inventors: Hans-Jürgen BUSCHMANN; Eckhard Schollmeyer
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: Huntsman Advanced Materials Switzerland GmbH
Priority date: 2000-12-07
Filing date: 2001-12-07
Publication date: 2003-09-10
Also published as: KR20030074646A; BR0115992A; CN1479822A; DE10060710A1; US20050260905A1; AU2002227995A1; WO2002046520A1

Abstract

The invention relates to a textile material, which is provided with a cyclodextrin finish and which has a polymer matrix that contains cyclodextrin and/or a cyclodextrin derivative. The invention also relates to a method for producing a textile material of this type.

Description

Textile material equipped with polymers Cvclodextrins and process for its production

The invention relates to a textile material with a cyclodextrin finish, a process for its production and its use.

Cyclodextrins are generally understood to be cycloamyloses or cycloglucans which are formed as cyclic dextrins when starch is broken down by Bacillus macerans or Bacillus circulans under the action of cyclodextrin glycosyltransferase. They consist of 6, 7 or 8 glucose units linked to form a cycle of αr-1, 4, as a result of which the α, β or cyclodextrins are defined. These are integrated in a crystal lattice and layered on top of one another in such a way that they form continuous inner-molecular channels in which they can include hydrophobic guest molecules in varying amounts until saturation, e.g. B. gases, alcohols or hydrocarbons. This process is referred to as "molecular encapsulation" (Römpp "Chemie Lexikon", Vol. 2, 1995, 9th extended edition). Because of this property, cyclodextrins are used for the production of foods, cosmetics, pharmaceuticals and pesticides, and for solid phase extraction.

It is known, for example, that cyclodextrins are used to convert compounds with low solubility into a soluble complex by complexation with cyclodextrins.

Reuber, A. et al. describe in the Journal of Inclusion Phenomena and Molecular Recognition in Chemistry 27 (1997), pp. 69-84 that dimeric cyclodextrins with high binding affinities for porphyrinoid photosensitizers as a carrier system can be used for the application of active substances in photodynamic cancer therapy.

Fujita, K. et al. describe in Tetrahedron Letters 25 (1984), pp. 5533-5536 the preparation of ditosylates of? -cyclodextrin and their purification by reverse phase chromatography.

WO 99/24474 discloses specific cyclodextrin oligomers which, by means of a spacer, consist of a rigid and preferably hydrophilic structural element and enable the detoxification of active pharmaceutical ingredients.

DE-A 198 25486 discloses absorbent polymers in which cyclodextrins or cyclodextrin derivatives are present ionically, covalently or by mechanical inclusion. These are used to hold aqueous liquids such. B. body fluids such. B. urine, in the hygiene field, as packaging material, as a carrier and / or as a stabilizer for fertilizers or as a soil conditioner.

In order to specifically change the properties of textile materials such as a fiber, a filament, yarn, pile or fabric, it is known to provide them with an equipment. This equipment can, for example, reduce wrinkles, reduce dirt or repel dirt. So cellulosic textile materials are generally equipped with a urea-formaldehyde product. This reduces the creasing ability of the material. Furthermore, equipment is known which improves the soiling behavior of the textile materials or the washing out of dirt therefrom. These so-called soil release finishing products are polymers. Examples include polyacrylates that are applied to the textile material during finishing. With this type of equipment, easier removal of the dirt is made possible and the penetration of the dirt into the textile material is also reduced. So-called stain repellency equipment can be used to prevent dirt from entering. This dirt-repellent finish provides the outside Surface of the textile material with a polymer protective layer. Fluorocarboxylic acids may be mentioned here as examples of such polymer compounds.

DE-A 40 35 378 discloses textile materials which are equipped with cyclodextrins or cyclodextrin derivatives and which serve to absorb non-polar dirt, sweat and sweat breakdown products or fragrances. The cyclodextile compounds are applied either directly by spinning in, a chemical or physical variant. The chemical variant takes place via a reaction of the textile material with linkage with the cyclodextrin compounds. If the linkage is not optimal, the cyclodextrins are washed out during chemical as well as physical anchoring. Chemical anchoring, in particular in the case of synthetic textile materials, is also often complex and / or cost-intensive.

There is therefore a need for synthetic and natural textile materials which have been stably modified with cyclodextrins.

It is accordingly an object of the present invention to provide a textile material with cyclodextrin or cyclodextrin derivatives on a permanent basis and to provide a process for its production.

The object is achieved according to the invention with a textile material with a cyclodextrin finish which has a polymer matrix which contains cyclodextrin and / or a cyclodextrin derivative.

The textile material according to the invention does not contain the cyclodextrin or predominantly not in a form chemically bound to the fiber, but in an applied and / or incorporated polymer matrix. The polymer matrix preferably contains the cyclodextrin as one of the basic building blocks, it being possible for further basic building blocks to be present for producing a chain or network structure. The production of the polymer matrix in the presence of the textile material is particularly preferred, so that the textile material itself and the polymer matrix form a structure which is interwoven. To this In this way, a highly cyclodextrin-containing textile material is produced without chemical bonding of the cyclodextrin. The risk of "washing out" the cyclodextrin-containing polymer matrix from the textile material, be it due to mechanical action, solution effects or hydrolysis effects of basic detergents, as in the case of textile materials finished with cyclodextrin in a known manner, no longer exists.

The proportion of polymer matrix containing cyclodextrin and / or cyclodextrin derivative is expediently 0.2 to 80% by weight, based on the textile material, preferably 1 to 40% by weight, based on the textile material, and particularly preferably 2 to 30% by weight .-%.

The amount of cyclodextrin and / or cyclodextrin derivative and thus the polymer matrix which contains the material equipped according to the invention is determined by the particular application of the material. The finished textile material according to the invention preferably has a proportion of 2 to 30% by weight and particularly preferably 7 to 20% by weight of cyclodextrin. Surprisingly, it was found that in the textile material equipped according to the invention with the polymer matrix there is a permanent improvement in the applications according to the invention. Thus, the cavities provided by the cyclodextrin compounds can serve to absorb liquids, gases and solids, such as cosmetics, pharmaceuticals, fragrances and flavorings.

Another object of the invention is to provide processes for producing the finished textile material. Here, in one

- First step on the textile material, an aqueous and / or organic solution of cyclodextrins and / or

Cyclodextrin derivatives applied with or without additives;

- partially dried in the second step; and - In the third step, the textile material is brought into contact with a second polymer-forming component and polymerized.

The aqueous or organic solution of cyclodextrin and / or cyclodextrin derivatives used in the first step contains the cyclodextrin or cyclodextrin derivative as the first polymer-forming component. It is understood that the cyclodextrins or their derivatives are polyfunctional, i.e. H. have at least two functions suitable for polymer formation. In addition, the solution may have other additives which are necessary for polymer formation or which promote polymer formation.

Suitable functions of cyclodextrin derivatives which are suitable for polymer formation include, in addition to the naturally present hydroxyl function, other functions which are suitable for crosslinking and which can be generated by converting or modifying the hydroxyl function in a manner known to the person skilled in the art. Such functions are, for example, halogen atoms, amino, carboxy, isocyanate and thiol groups.

In the context of the invention, the term “cyclodextrins” is understood to mean α-, β- or cyclodextrin.

The term “cyclodextrin derivatives” in the context of the invention is understood to mean functionalized and derivatized cyclodextrins, including partially methylated, ethylated and otherwise substituted ones.

In the context of the invention, the term “textile material” means that the textile materials represent, for example, fibers, filaments, yarns, piles or fabrics.

The textile material is understood to mean natural as well as synthetic or synthetic fiber-containing materials. Cotton, wool, linen or silk are understood as natural textile materials. Cellulose-based textile fibers are cotton, linen, cellulose or Artificial silk. This also includes viscose, cupro and acetate. The term "synthetic fibers" is understood to mean fully synthetic fibers which are produced from simple building blocks by polymerization, polycondensation or polyaddition. These include elastane, elastodiene, fluorofibre, polyacrylic, modacrylic, polyamide, aramid, polyvinyl chloride, polyvinylidene chloride, polyester, polyethylene, polypropylene and polyvinyl alcohol. The synthetic fiber-containing materials are those which contain both the purely synthetic fiber and natural materials such as those based on cellulose. The textile materials finished according to the invention are in particular also those made of synthetic fibers which have no groups reactive towards the polymer building blocks of the cyclodextrin polymer.

In particular, polyalcohols, polyamines or other polyfunctional molecules with at least two functions suitable for crosslinking are suitable as the second polymer-forming component. For a flexible product, the use of chain lengths of C ₂ to C ₂ , in particular C to C 10, these crosslinkers is preferred, aliphatic polyfunctional crosslinkers being preferred over aromatic ones. Further examples of the second polymer-forming component are the - and / or polyfunctional compounds, such as dicarboxylic acids, dicarboxylic acid anhydrides, diisocyanates, aminocarboxylic acids, diols, diamines or thiols. Furthermore, 1,3,5-trichloro-2,4,6-triazine, 2,3-dichloroquinoxaline-5- and -6-carboxylic acid chloride and chloro-difluoropyrimidine are also suitable. Crosslinking of cyclodextrins can also be brought about with alkoxysilanes or alkoxysiloxanes, in particular silanes and siloxanes with two or more alkoxy groups. The ethoxy compounds are preferred.

The textile materials finished according to the invention are in particular also those made of synthetic fibers which have no further reactive groups which could intervene in the polymerization process. The two-stage manufacturing process described above is particularly suitable for this. When the two-stage process is used on textile materials which contain reactive groups, such as in particular on cellulose-based textile fibers, chemical bonds between the cellulose material and the polymer building blocks naturally also occur to a considerable extent, so that the formation of the separate polymer matrix can step into the background compared to the binding.

This last-described aspect is avoided with a further process variant, according to which a mixture of a cyclodextrin and / or cyclodextrin derivative and a second polymer-forming substance, optionally dissolved in an inert solvent, is applied to a textile material to complete the crosslinking under crosslinking conditions and with crosslinking already taking place becomes.

In this process variant, cyclodextrin and a second polymer-forming component reactive therewith, for example a diisocyanate, a dicarboxylic acid dichloride, a dicarboxylic acid anhydride or the like, are expediently mixed with any necessary customary auxiliaries, for example catalysts, and, if appropriate, dissolved in an unreactive solvent, so that the crosslinking reaction begins. The mixture in the crosslinking is then applied to the textile material in a conventional manner and introduced into it, for example by spraying or soaking, so that the crosslinking can take place.

Cyanuric chloride is particularly suitable for this reaction. Particularly preferred materials for the second component are di- and polyisocyanates in their monomeric or oligomeric forms, for example hexamethylene diisocyanate, isophorone diisocyanate, or also MDI or TDI. Mixing of the two components and application are coordinated with one another in such a way that partial contact (prepolymer formation) has already taken place on contact with the textile material and the final crosslinking itself takes place on and in the textile material. If small amounts of water are added (less than 1% by weight, preferably 0.2 to 0.5% by weight), foaming can additionally be achieved.

In principle, the polymerization of the components provided for this takes place before, during and after application to the textile material at the usual temperatures and time frame provided for the materials. Removal of solvents or solvent residues, if required, takes place at the normal temperatures which are acceptable for the textile material.

This one-step process is also particularly suitable for forming a polymer matrix in textile materials made from natural fibers, which contain reactive hydroxyl or amino functions. The relatively rapid onset of crosslinking, separate from the textile material, is suitable for limiting the reaction of the crosslinking agent with the textile material to such an extent that a polymer matrix is predominantly formed and only a relatively small number of connection points are formed with the textile material.

In the multi-stage process, the first reaction step takes place, for example, at temperatures between 40 to 140 ° C., preferably between 50 to 90 ° C. in the aqueous and / or organic solution which contain the cyclodextrins or cyclodextrin derivatives. Polar solvents are used as solvents. Examples include water, lower alcohols, amines or dimethylformamide. Water or an alcohol from the group of methanol, ethanol, propanol, isopropanol or butanol is preferably used.

The solvent is then removed in a drying step in a temperature range from 60 to 150 ° C.

The treatment time in the multi-stage process depends on the textile material used and the treatment temperature and can vary in a range from 5 minutes to 120 minutes.

After the drying step, the pretreated textile material is wetted with the polymer-forming component and the polymerization reaction of the polymer-forming component into a three-dimensional polymer matrix. The temperature of the final formation of the polymer matrix depends on the reactivity of the polymerization reaction and can already take place at room temperature. Depending on the monomer component used, an elevated temperature of up to 150 ° C may also be required. The reaction time of the third step of the actual formation of the polymer matrix and simultaneous linking of the resulting Polymer matrix with the textile material is also dependent on the reactivity of the monomers and is in an interval of 2 to 120 minutes.

The textile material which contains the polymer matrix according to the invention is constructed in such a way that the polymer matrix forms a "mixed fabric" with the existing textile material, which contains the cyclodextrin in the polymer matrix as a building block.

Dimethylolurea (DMU), dimethoxymethylurea (DMUMe2), methoxymethyl-melamine, dimethylolethylurea (DMEU), dimethylol-dihydroxyethylene urea (DMDHEU), dimethylol-propyleneurea (DMPU), dimethoxethylamethylurea, dimethyloxymethylurea, also can be used as the second polymer-forming component. or methylolacrylamide can be used. These polymer-forming components react with the hydroxyl groups of the cyclodextrins or cyclodextrin derivatives to form the polymer matrix. A two- or three-dimensional polymer matrix is created. Since these polymer-forming components also react with the hydroxyl functions of cellulose-containing materials, their use in the one-step mixing process or, as far as the multi-step process is concerned, on textile materials made from unreactive synthetic fibers is preferred.

The polymer matrix of the textile material can, for example, be in the form of a polyester and can be produced as a second monomer via a polycondensation reaction of cyclodextrin with, for example, a dicarboxylic acid or its derivative. Extensive spatial networking is ensured via the numerous hydroxyl functions of cyclodextrin. The reaction of the cyclodextrins with polyisocyanates is a polyaddition.

It goes without saying that functionally modified cyclodextrins can also be used according to the invention, for example cyclodextrins which have isocyanate, amino, thiol, carboxyl or functions derived from carboxyl groups, by way of a polyaddition reaction to give polyurethanes. These can be done in a manner known per se to the person skilled in the art can be reacted with appropriate crosslinkers to give the desired polymer matrix.

When the corresponding polyisocyanates are reacted with water and / or polycarboxylic acids, for example, a polymer can be produced which adheres to the textile material in the form of a fine foam and leads to an arrangement of the cyclodextrin units close to the surface and easily accessible.

Another object of the invention is the use of the textile materials produced by the method in the delivery of pharmaceutically active substances and for the delivery of cosmetics and fragrances and perfumes.

Another application is in the field of medical diagnostics. So z. B. organic components of sweat are collected and analyzed.

In a further application, the textile materials produced by the method according to the invention can be used for the storage of pollutants from the air. It is also possible to use any type of filter on a wide variety of nonwovens or fabrics. In addition, the textile materials can also be used for the storage of hydrophobic or partially hydrophobic substances from an aqueous phase in wastewater and water purification and for the purification and concentration of substances, such as metals.

The textile materials used in the field of filter application can preferably have a rigid design of the textile material as well as a higher loading with cyclodextrin, cyclodextrin derivatives or mixtures thereof. Preferred materials are those which have a fine foam on the surface of the textile material in order to additionally enlarge the surface. Surprisingly, it was found that the textile materials finished according to the invention ensure extremely long use for each of the applications, since the cyclodextrin building blocks remain stably bound in the matrix and hydrolysis phenomena are less susceptible.

embodiments

example 1

A cotton and a polyester standard fabric with a basis weight of 100 g / m ² were padded with the following liquor, the textile material first being immersed in the liquor for 2 minutes and then padding for 3 m / min at a line pressure of 50 kp / cm ² has been. The fabric treated in this way was condensed after drying for 90 minutes at 150 ° C. over a period of 2 minutes. The basic composition of the fleet consisted of dimethylol urea in an amount of 50 g / l magnesium chloride hexahydrate in an amount of 10 g / l, ammonium sulfate in an amount of 1 g / l and? -Cyclodextrin. Six basic compositions were prepared in which the? -Cyclodextrin was mixed in amounts of 0 g / l, 10 g / l, 20 g / l, 30 g / l, 40 g / l and 50 g / l.

The tissue samples previously equipped with cyclodextrin and the polymer-forming component were then immersed in a standard solution of butyric acid (10 g / l). After squeezing and rinsing, the remaining butyric acid concentration was determined by gas chromatography. This shows that with the increasing concentration of ^ -cyclodextrin larger amounts of butyric acid were taken up, which was accompanied by a decrease in the butyric acid concentration, as can also be seen in FIG.

In addition, the finished tissue samples were washed fifty times each according to the conditions described above. Afterwards, these materials were immersed again in the standardized butyric acid solution, squeezed and rinsed. There was again the reduction of Concentration of the butyric acid solution observed. The measured values in the fleet corresponded to those of the first measurement.

Both textile materials gave essentially the same results.

Example 2

Example 1 was repeated with the same cotton and polyester standard fabric, but was first treated with the cyclodextrin solution, then gently dried and then impregnated with a liquor composed of dimethylolurea, magnesium chloride hexahydrate and ammonium sulfate. After drying again under gentle conditions, condensation was carried out under standard conditions.

The standard polyester fabric resulted in a product that contained the cyclodextrin fully incorporated into the polymer matrix. The cotton standard fabric still contained numerous bonds of the polymer matrix to the fiber, although the cyclodextrin was predominantly in the polymer matrix.

Example 3

The fabrics of Example 1 were impregnated with a mixture of 10 g / l ^ cyclodextrin and 5 g / l hexamethylene diisocyanate with an amine catalyst (DMDEE) in methylene chloride. The mixture was prepared immediately before it was used and applied when the crosslinking reaction proceeded.

A polymer matrix was obtained in both fabrics, which ran through the textile material without being appreciably chemically bound to it.

Claims

claims

1. Textile material with a cyclodextrin finish, so that it has a polymer matrix that contains cyclodextrin and / or a cyclodextrin derivative.

2. Textile material according to claim 1, characterized in that the proportion of the polymer matrix is 0.2 to 80 wt .-%, based on the textile material.

3. Textile material according to claim 1 or 2, characterized in that the proportion of the polymer matrix is 1 to 40 wt .-% and particularly preferably 2 to 30 wt .-%, based on the textile material.

4. Textile material according to claim 1, characterized in that the cyclodextrin is ^ cyclodextrin.

5. Textile material according to claim 1, characterized in that the proportion of cyclodextrin 2 to 30 wt .-%, based on the textile material, and preferably 7 to 20 wt .-%.

6. Textile material according to one of the preceding claims, characterized in that the polymer matrix is a cyclodextrin-containing polyester or such a polyurethane.

7. Textile material according to one of claims 1 to 5, characterized in that the polymer matrix is obtainable by crosslinking cyclodextrin with a polyalcohol, a polycarboxylic acid, a polyisocyanate, an alkoxysilane or siloxane or with cyanuric chloride.

8. Process for producing the textile material according to one of the

Claims 1 to 7, characterized in that in one

first step, an aqueous and / or organic solution of cyclodextrin or cyclodextrin derivative with or without additives is applied to the textile material;

partially dried in the second step; and

in the third step, the textile material is brought into contact with a second polymer-forming component and polymerized.

9. The method according to claim 8, characterized in that when applying the cyclodextrin or cyclodextrin derivative in the first step there is no chemical bonding of the cyclodextrin to the textile material.

10. The method according to claim 8, characterized in that is used as cyclodextrin or cyclodextrin derivative.-Cyclodextrin or a ^ -cyclodextrin derivative.

11. The method according to claim 8, characterized in that as cyclodextrin derivatives those with Cι_-i4-alkyl, carbonyl, carboxyl, isocyanate,

Thiol or amino groups can be used.

12. The method according to claim 8, characterized in that natural or synthetic materials are used as textile materials.

13. The method according to claim 8, characterized in that textile materials are understood to be those from the group of fibers, filaments, yarns, piles or fabrics.

14. A method for producing the textile material according to one of claims 1 to 7, characterized in that in a first step

Mixture of a cyclodextrin and / or cyclodextrin derivative and a second polymer-forming component, optionally dissolved in an inert solvent, is applied to a textile material under crosslinking conditions and with crosslinking already taking place, and the textile material is dried in a second step.

15. The method according to claim 14, characterized in that natural textile materials are used.

16. Use of the textile material according to one of the preceding claims in the delivery of pharmaceutically active substances, for the release of fragrances and perfumes, in the field of medical diagnostics and for the storage of pollutants from liquid or gaseous media.