DE19520967A1 - Treatment of leather, synthetic or natural textiles - Google Patents

Abstract

Textile material or leather treated with 0.1-25 wt.% one or more reactive cyclodextrin deriv. (C) contg. at least one N heterocycle, is claimed. The prepn. of this material/leather is also claimed, by dissolving (C) in suitable reaction medium and adding bases and opt. salts or additives, applying the neutral to basic soln. to the material/leather, opt. drying, and fixing at 20-220 deg C.

Description

The invention relates to textile material or leather, which with reactive cyclodextrin derivatives with at least one nitrogen-containing heterocycle.

There are already a number of reactive cyclodextrin drugs ten and methods for their preparation are known. So be EP-A-483380 from Toppan Printing writes a metho de for the production of cyclodextrin-containing polymers in which Aldehyde groups in protected or unprotected form Cyclodextrin are introduced, which then with the nucleophi len hydroxyl groups of a polymer react. The connection of cyclodextrins to polymers via an acetal bond, such as described in patent application EP-A-483380 is because of the known lability of acetals under acidic conditions not advantageous.

A. Deratani and B. Pöpping (Makromol. Chem., Rapid Commun. 13, 237-41 (1992)) describe the preparation of a cyclodextrin-chlorohydrin (3-chloro-2-hydroxypropyl-cyclodextrin derivative) by reacting β- Cyclodextrin in an aqueous medium with epichlorohydrin under Lewis acid conditions with Zn (BF₄) ₂ as a catalyst. Under basic conditions, this derivative is capable of nucleophiles such as. B. OH ^- ions (sodium hydroxide solution) to react. Disadvantageously, only a very slight incorporation of epichlorohydrin was achieved in the reaction of cyclodextrin with epichlorohydrin under Lewis acidic conditions. It was therefore necessary to work with a very high excess of epichlorohydrin, which inevitably leads to a large amount of extremely toxic or carcinogenic by-products which have to be separated off and destroyed.

DE 40 35 378 describes a textile material, in particular a Fiber, filament, yarn, pile or sheet Chengestilde disclosed with equipment in which minde least a cyclodextrin or cyclodextrin derivative chemically and / or is physically fixed to the textile material. In addition, a method for producing such textile materials described.

The present invention relates to textile material, in particular especially a fiber, a filament, a yarn, a pile or a fabric, or leather, which is 0.1 to 25 % By weight, based on the weight of the untreated material with at least one reactive cyclodextrin derivative equipped with at least one nitrogen-containing heterocycle is.

The textile material or leather is preferably 0.3 to 10% by weight of the cyclodextrin derivative mentioned.

The equipment is preferably in the outdoor areas the fibers or the material.

The equipment is made via covalent bonding of the reactive Cyclodextrin derivatives. This results in great wet fastness and wash resistance.  

The finishing of textile materials or leather with reactive cyclodextrin derivatives with at least one stick Heterocycle containing substances is analogous to that in the Tex til / leather industry usual methods for reactive dyes with the corresponding reactive groups.

Examples of suitable textile materials for finishing are:
Cellulose fibers, especially cotton, regenerated cellulose (e.g. viscose or artificial copper), fiber blends with cellulose or wool, especially sheep's wool, and polymer fibers such as polyester, polyamide or polyacrylonitrile with at least one nucleophilic group such as OH, SH or NH or fiber blends with these polymer fibers.

The invention further relates to methods for producing the materials according to the invention. The production takes place before preferably by means of a method which is characterized thereby is that reactive cyclodextrin derivatives, which in fol be described in more detail in a suitable reak tion medium (liquor) with the addition of bases and possibly of Salts and additives to the reaction medium dissolved, in neutral to basic milieu on the materials or leather applied the materials or the leather if necessary dried and then fixed at temperatures of 20-220 ° C. will.

Applying the fleet to the materials or leather can be done in a batch process (pull-out process) the fixation is done by heating the liquor or in semi-continuous dwell process or in continuous Chen procedures in which the fixation outside the fleet on the (impregnated), soaked with the fleet, if necessary dried material is analogous to that for coloring  textile materials or leather developed dyeing techniques. Fixation is particularly efficient with the last two Procedure if the textile material before fixing through Squeezing largely freed from the fleet or even ge was dried. Then there is a thorough rinsing the materials with cold and / or hot water and possibly washing the materials with an effective detergent at the appropriate temperature in an otherwise known manner and Wise.

As reactive cyclodextrin derivatives with nitrogenous Heterocycle to equip the textile material or Such cyclo derivatives are preferably used in leathers whose nitrogen-containing heterocycle is one to three electrophilic Centers.

The electrophilic centers can be the same or different be and are carbon atoms on which halogen, in particular F, Cl, or an ammonium substituent, especially tri alkylammonium or a substituted or unsubstituted Pyridinium substituent, is covalently bonded.

The distribution of substituents on the cyclo dextrin is preferably unselective.  

The cyclo used according to the invention are preferably sufficient dextrin derivatives of the following formula I:

where R is OH or OR¹ or R² and
R¹ is a hydrophilic residue which may be the same or different and
R² is a nitrogen-containing heterocycle which is either directly attached or is attached via a spacer by means of an ether, thioether, ester or amine bond,
wherein the spacer is an alkyl or hydroxyalkyl radical with 1-12 carbon atoms which is bonded to the anhydroglucose via an ether, thioether, ester or amine bond and
the nitrogen-containing heterocycle comprises at least one halogen or one ammonium substituent and is present at least once per cyclodextrin and
n means 6, 7 or 8.

Preferably R1 is the same or different and means Methyl, ethyl, n- or i-propyl, n- or i-butyl, C₂-C₆- Hydroxyalkyl such as hydroxyethyl, hydroxy-i-propyl, hydroxy-n- propyl, C₃-C₆-oligohydroxyalkyl such as dihydroxy-i-propyl, Dihydroxy-n-propyl, C₁-C₄-carboxyalkyl (in the form of the free Acid or as alkali salt) such as carboxymethyl, Carboxyethyl, carboxy-i-propyl, carboxy-n-propyl or a Alkali salt of the carboxyalkyl substituents mentioned, acetyl, Propionyl, butyryl, sulfate, C₁-C₄ sulfonic acid alkyl (in the form the free acid or as an alkali salt), C₂-C₄-carboxyhydroxy alkyl (in the form of the free acid or as an alkali salt), C₂-C₄- Sulphonic acid hydroxyalkyl (in the form of the free acid or as Alkali salt) and oxalyl, malonyl, succinyl, glutaryl, Adi pinyl (in the form of the free acid or as an alkali salt).

Preferably R² is the same or different and means

-R³ _m - (CHR⁴) _o -R⁵-R⁶,

in which
R³ is the same or different and

means and
R⁷ is the same or different and is C₁-C₆ alkyl and
R⁴ is the same or different and is H or OH and

is particularly preferably O, and
R⁶ in the event that R⁵ NH, NR⁷, S, or O means either

is
wherein R⁸ and R⁹ are the same or different and are Halo gene, preferably Cl or F, or
R⁸ NR¹⁰R¹¹, OH, OAlkali, OR⁷, O (i-C₃H₆), OCH₂CH₂OCH₃, SO₃H means and
R⁹ halogen, in particular Cl or F, or ammonium substituent, in particular trialkylammonium or substituted or unsubstituted pyridinium substituents, such as. B.

means and
R¹⁰ is hydrogen or an aliphatic radical, preferably a C₁-C₄-alkyl radical which is OCH₃, OC₂H₅, COOH, OSO₃H, SO₃H, OCH₂CH₂SO₂CH₂CH₂OSO₃H, OCH₂CH₂SO₂CH = CH₂, OCH₂CH₂SO₂CH₂CH₂Cl, SO₂CH₂CH₂CH₂oOpip, we to 6-membered cycloalkyl radical or araliphatic radical, preferably radicals of the formula

means
where p = 1-4 and the radical A can be substituted, for example, by Cl, NO₂, COOH, SO₃H, CH₃, OCH₃, SO₂CH₂CH₂OSO₃H, SO₂CH = CH₂, CH₂SO₂CH₂CH₂OSO₃H, CH₂SO₂CH = CH₂, and
R¹¹ has the meanings mentioned for R¹⁰ or phenyl radical or substituted phenyl radical, preferably substituted by Cl, NO₂, COOH, SO₃H, CH₃, OCH₃, SO₂CH₂CH₂OSO₃H, SO₂CH = CH₂, CH₂SO₂CH₂CH₂OSO₃H, CH₂SO₂CH = CH₂ or R⁶

is where
R¹², R¹³ and R¹⁴ are identical or different and are preferably halogen or Cl or F,
or R⁶ in the event that R⁵

means

or

means and
o is an integer from 0 to 12 and
m is 0 or 1, where
for o = 0 also m = 0 applies.

The following cyclodextrin derivatives are particularly preferred Equipment of the textile materials or the leather turned on sets: 2,4-dichloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-  hydroxy-1,3,5-triazinyl-cyclodextrins (sodium salts), 2- Fluoro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (sodium Salts), 2,4,5-trichloropyrimidyl cyclodextrins, 5-chloro-2,4- difluoropyrimidyl cyclodextrins, 6- (2,3-dichloro) quinoxali noyl cyclodextrins, 5- (2,4-dichloro) pyrimidinoyl cyclodex trine, 2-amino-4-chloro-1,3,5-triazinyl-cyclodextrins, 2- Chloro-4-ethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4- diethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4- methoxy-1,3,5-triazinyl-cyclodextrins.

2-Chloro-4-hydroxy-1,3,5-tri is particularly preferred azinyl-β-cyclodextrin (HCT-β-CD) used.

Cyclodextrin derivatives with a DS are preferred (average degree of substitution per anhydroglucose) to DS 3.0, particularly preferably DS 0.2 to 2.0, in particular preferably DS 0.3 to 1.0 for reaction with the textile Material or leather used.

The preparation of the Cyclodex used according to the invention trine is preferably carried out by means of a process which is characterized in that native α-, β- and / or γ- Cyclodextrin and / or a suitable α-, β- and / or γ- Cyclodextrin derivative in a suitable reaction medium in Presence of an acid acceptor and optionally one surfactant in weakly acidic to strong base suitable environment at temperatures from -10 to + 70 ° C with suitable nitrogenous heterocycles implemented and possibly on closing in the neutral or weakly basic area if necessary with the help of a buffer in an otherwise known manner and way is worked up.  

The cyclodextrin derivative obtained can then optionally by means of a cleaning process customary for cyclodextrin derivatives be cleaned further.

With the method, cyclodextrin derivatives with sta bile C-O, C-S or C-N bonds, none toxic compounds occur as in the known Ver drive by reacting cyclodextrin with epichlorohydrin. So fall z. B. in the implementation of cyclodextrin Cyanuric chloride only table salt and toxicologically essential more worrying by-products.

Any cyclodextrins or cyclo are suitable for the process dextrin derivatives which have at least one free OH group / Cyclodextrin molecule in at least one of the positions C2, C3, and / or C6 of anhydroglucose are suitable. Cyclo Dextrin or cyclodextrin derivative do not have to be special Purity requirements are met. You are in han standard quality with a water content of 0 to 16% applicable.

Examples of cyclodextrin derivatives that are used in the manufacture are suitable, cyclodextrin ethers or Mixed ethers, cyclodextrin esters or mixed esters or mixed Cyclodextrin ether / ester derivatives, especially those mentioned Derivatives of β-cyclodextrin.

Hydrophilic cyclodextrin derivatives are particularly suitable with the following substituents: (C₁-C₄) alkyl, preferred Methyl or ethyl radical, particularly preferably methyl radical; (C₂- C₆) -Hydroxyalkylrest, preferably hydroxypropylrest or Hydroxybutyl radical, particularly preferably hydroxypropyl radical, (C₃-C₆) -Oligohydroxyalkylrest, preferably C₃-C₄, especially preferably dihydroxypropyl radical, acetyl radical, propionyl radical,  Butyryl radical, preferably acetyl radical, propionyl radical, particularly preferably acetyl radical.

Derivatives with an average are preferably suitable degree of substitution per anhydroglucose (DS) of 0.3 2.0 particularly preferably from 0.6-1.8.

Ionic cyclodextrin derivatives are also particularly suitable te with the following substituents: carboxyalkyl radical in the form of free acid or as alkali salt, sulfonic acid alkyl residue in Form of the free acid or as an alkali salt, carboxyhydroxy alkyl radical in the form of the free acid or as an alkali salt, Sulphonic acid hydroxyalkyl radical in the form of the free acid or as alkali salt, (C₁-C₄) alkyl, (C₂-C₄) hydroxyalkyl and sulfate residue.

In these cyclodextrin derivatives, the is preferably average degree of substitution per anhydroglucose (DS) 0.3-2.0, particularly preferably 0.4-1.5, in particular 0.4- 0.6.

Ionic cyclodextrin derivatives are also particularly suitable vate with oxalyl, malonyl, succinyl, glutaryl and / or adipinyl as substituents, preferably with an average degree of substitution per anhydrogluco se (DS) from 0.3 to 2.0, particularly preferably 0.4-1.5, especially 0.4-0.8.

The preparation of the suitable cyclodextrin derivatives is known from the literature.

Nitrogen-containing hetero are for use in the process cycles with at least two electrophilic centers are suitable.  

Examples of such heterocycles are 2,4,5,6-tetrachlor pyrimidine, 2,4,6-trifluoro-5-chloropyrimidine (can be prepared from 2,4,5,6-tetrachloropyrimidine by halogen exchange); 2.4- Dichloropyrimidine-5-carboxylic acid chloride (can be produced from methods known from the literature); 2,3-dichloroquinoxaline-6-car bonic acid chloride (manufactured according to K.G. Kleb, E. Seal, K. Sasse, Angew. Chem. 76, 423 (1964); Appl. Chem. Int. Ed. Engl. 3, 408 (1964)) and those shown below Compounds of formula II

where X and Y can be the same or different and halo gene, preferably F or Cl and Z halogen preferably F or Cl, OH, OLi, ONa, OK, OR⁷, SR⁷, or NR¹⁰R¹¹, where the radicals R⁷ to R¹¹ have the meaning already mentioned to have.

Examples of compounds of formula II are 2,4,6-trichloro-1,3,5-triazine; 2,4,6-trifluoro-1,3,5-triazine; 2-amino-4,6-dichloro-1,3,5-triazine; 2,4-dichloro-6-methoxy 1,3,5-triazine; 2,4-dichloro-6-hydroxy-1,3,5-triazine, or that Sodium salt of this compound, 2,4-dichloro-6-ethylamino 1,3,5-triazine, 2,4-dichloro-6-diethylamino-1,3,5-triazine.

The compounds mentioned are commercially available or by known or analogous processes from the 2,4,6-tri chloro-1,3,5-triazine by reaction with the corresponding Nucleophiles available.  

2,4,6-Trichlor-1,3,5-triazine; 2,4,6-tri fluoro-1,3,5-triazine; 2-amino-4,6-dichloro-1,3,5-triazine; 2.4- Dichloro-6-methoxy-1,3,5-triazine; 2,4-dichloro-6-hydroxy 1,3,5-triazine, sodium salt; 2,4,5,6-tetrachloropyrimidine; 2,4,6-trifluoro-5-chloropyrimidine; 2,4-dichloropyrimidine-5- carboxylic acid chloride or 2,3-dichloroquinoxaline-6-carboxylic acid chloride 2,4-dichloro-6-ethylamino-1,3,5-triazine, 2,4-dichloro- 6-diethylamino-1,3,5-triazine used.

As a reaction medium for the process according to the invention preferably DMF (dimethylformamide), DMSO (dimethyl sulfate oxide), xylene, dioxane, acetone, methanol, ethanol, water, Toluene, methyl ethyl ketone or mixtures of these substances is suitable.

When reacting with 2,4,6-trihalo-1,3,5-triazines preferably cyanuric chloride, should the heterocycle in fine dis Persian form, in the form of mixtures with organic Solvents or in water if necessary with the addition of an upper surfactants as wetting agents.

Water or a water / acetone gel is particularly preferred used in a mixing ratio of 10: 1 to 2: 1.

In the process, one or. Is preferably used as the acid acceptor several substances selected from the group of alkali or alkaline earth hydroxides, alkali or alkaline earth carbonates, Alkali or alkaline earth hydrogen carbonates, alkali hydrogen phosphates, amines, tert. Amines, pyridine suitable.

NaOH, KOH, sodium carbonate, potash is particularly preferred umcarbonate, sodium bicarbonate, potassium bicarbonate, Disodium hydrogen phosphate, dipotassium hydrogen phosphate, pyri din, triethylamine or collidine used.  

As a surface active agent in this process are the suitable for reactions with cyanuric chloride. Examples of such agents are alkyl sulfates and ethers sulfates as sodium, ammonium, lithium and triethanol ammonium salts (available, for example, from Hen kel, Düsseldorf under the name Texapon), or nonyl phenol polyglycol ether or mixtures of anionic and nonionic surfactants (available for example from Atlas Chemie, Essen under the name Renex and Atlox) or alkyl sulfonates.

Texapon K12, Renex 697 and Atlox are particularly suitable 4853B, sodium dodecyl sulfate, sodium octyl sulfate, 1-dodecane sulfonic acid sodium salt, 1-octanesulfonic acid sodium salt (The latter is available, for example, from Fluka Fein chemicals GmbH, Neu-Ulm).

As a buffer in the process for the pH range from 6 to 10, preferably 7 to 9, generally used buffers puts. Such buffers are, for example, phosphate buffers (e.g. Na₂HPO₄ / KH₂PO₄), carbonate buffer (e.g. Na carbonate / Na bicarbonate), acetate buffer (e.g. acetic acid / Na acetate), Citrate buffer (e.g. citric acid / Na citrate) or tris Buffer (e.g. trishydroxymethylaminomethane / HCl).

Cyclodextrin is preferred per mole of anhydroglucose 0.1-4 mol, preferably 0.2-2 mol, particularly preferably 0.3-1.2 mol, nitrogen-containing heterocycle used. The turned set molar ratios are depending on the desired Degree of substitution and water content of the Cyclodex used trins selected.

Preferably, per mole of nitrogen-containing heterocycle 0.5-3 mol, acid acceptor used.  

For the representation of monohalotriazinyl-cyclodextrin deri 2,4,6-trihalo-1,3,5-triazines are made 1.5-4 mol, preferably 1.75-3.5 mol, particularly preferably 1.8-3.2 mol, Acid acceptor per mole of nitrogen-containing heterocycle puts.

For the representation of monohalotriazinyl-cyclodextrin deri Data from dihalo-1,3,5-triazines are preferred 0.5-2 mol 0.75-1.5 mol, particularly preferably 0.8-1.3 mol, of acid Acceptor used per mole of nitrogen-containing heterocycle.

For the representation of Trihalopyrimidyl-Cyclodextrin-Deri vaten be 0.5-1.5 mol, preferably 0.75-1.25 mol, esp ders preferably 0.8-1.2 mol, acid acceptor per mol stick heterocycle containing substance.

For the preparation of dichloro-quinoxalinoyl or dichloro pyrimidinoyl-cyclodextrin derivatives are 0.5-2 mol, before preferably 0.75-1.5 mol, particularly preferably 0.8-1.3 mol, Acid acceptor per mole of nitrogen-containing heterocycle puts.

Cyclodextrin or cyclodextrin derivative are preferred and reaction medium in a cyclodex ratio trin / reaction medium from 1: 30 to 1: 1.5, preferably about 1:14 to 1: 2, particularly preferably 1:12 to 1: 3.

To prepare the appropriate cyclodextrin derivatives Cyclodextrin or cyclodextrin derivative, containing nitrogen Heterocycle, acid acceptor, reaction medium and possibly upper surfactant, in the specified proportions put together either simultaneously or in succession and well stirred.  

In the process it is important that the reaction medium is not gets too sour.

The procedure should be used when converting cyclodextrin or Cyclodextrin derivative with trihalotriazine for the preparation of Monohalotriazinyl cyclodextrins at -10 ° C to 35 ° C before draws -5 ° C to 25 ° C, particularly preferably -5 ° C to 15 ° C, be performed.

The implementation of cyclodextrin or cyclodextrin derivative with Trihalotriazine for the preparation of Dihalotriazinyl-Cyclodex trine, should at -10 ° C to 25 ° C, preferably -5 ° C to 10 ° C, particularly preferably -5 ° C to 5 ° C, take place.

The implementation of cyclodextrin or cyclodextrin derivative with Tetrahalopyrimidine, at 10 ° C to 45 ° C, should be preferred 15 ° C to 35 ° C, particularly preferably 20 ° C to 35 ° C, take place.

The implementation of cyclodextrin or cyclodextrin derivative with heterocyclic acid chlorides takes place at temperatures of 20 to 90 ° C, especially at 30 to 80 ° C, especially at 40 up to 70 ° C.

The process is advantageously carried out at normal pressure guided.

The response times are usually between 0.5 and 6 h, often between 2-4 h.

Mixtures are preferably obtained by means of the process of cyclodextrin derivatives with an average sub Degree of substitution (DS) for R¹ from 0 to 2.0 depending on the as Starting product used Cyclodextrin / Cyclodextrinderi vat and a (DS) for R² from 0.1 to 3.0.  

The determination of the average degree of substitution per anhydroglucose (DS value) for nitrogenous substi can do according to methods known from the literature about elements tar analysis, such as in US 5,134,127 and US 3,453,257 for sulfur- or nitrogen-containing substituents described.

The reactive centers per anhydroglucose can be determined by reacting the cyclodextrin derivatives with nucleophiles, as described in the examples with chlorine as the starting group as DS _Cl .

Further processing of the cyclodextrin derivatives can if desired, with general for cyclodextrin cleaning my known methods are done. Such methods are included for example: precipitation using alcohol / water mixtures, direct crystallization, adsorption chromatography or Gel permeation chromatography and dialysis.

The reactive cyclodextrin which can be prepared as described Derivatives are analogous to the reactive dyes on the Fiber or leather. It is preferably used for this the usual dyeing in dyeing with reactive dyes seem. Depending on the reactivity, a distinction is made between Cold fixers and hot fixers. These differ in the reactivity of the reactive group.

Cold fixers include cyclodextrin derivatives with di chlorotriazine, monofluorotriazine, dichloroquinoxaline, di fluorochloropyrimidine and vinyl sulfone groups to the hot fix the monochlorotriazines and the trichloropyrimidines. The cyclodextrin deri which is particularly preferred according to the invention vat 2-chloro-4-hydroxy-1,3,5, -triazinyl-β-cyclodextrin,  Sodium salt (MCT-β-CD) therefore belongs to the group of Heat fixer and is therefore somewhat reactive.

For the finishing of leather are especially the di and Monochlorotriazine, pyrimidine cyclodextrin derivatives or Cyclodextrin derivatives with vinyl sulfonic acid groups are suitable.

A suitable dyeing technique is, for example, in Ullman's Encyclopedia of Industrial Chemistry 5th edition, Vol. A 22, page 662.

For finishing textile materials or leather with A distinction is made between reactive cyclodextrin derivatives 3 Fixing procedure:

1. Extraction process or batch process

With this process, loose materials such as yarn or Piece goods treated (e.g. textile fabrics: yarn, knitted and Knitwear, pile fabrics, terry goods, fiber blends). The cyclodextrin derivatives are applied in the Brine by heating. Bases and possibly salts and additives are either completed at the start of the fleet process added or in portions during the process after be added time and temperature.

Reaction parameters for the cold fixers

20-60 ° C, preferably 30-50 ° C
pH = 9-12, preferably pH = 10-11
Total reaction time 0.1-4 h, preferably 0.2-2 h.

Reaction parameters for the heat fixers such as B. MCT-β-CD

20-100 ° C, preferably 50-98 ° C
pH = 10-13, preferably pH = 11-12
Total reaction time at a fixing temperature of 90-98 ° C, 0.1-4 h, preferably 0.2-1.5 h
Total reaction time at a fixing temperature around 25 ° C, 5-40 h, preferably 7-25 h.

2. Semi-continuous dwell process

This process treats piece goods (e.g. cellulo se piece goods). The material is impregnated with the fleet, fixation takes place outside the fleet at room temperature structure or by heating after the textile material has passed through Squeeze dried to a certain liquor content has been.

Reaction parameters for the cold fixers

pH = 9-12, preferably pH = 10-11
Residence time at 18-60 ° C, preferably 20-40 ° C outside the liquor 1-10 h, preferably 2-8 h.

Reaction parameters for the heat fixers such as B. MCT-β-CD

20-100 ° C, preferably 50-98 ° C
pH = 10-13, preferably pH = 11-12
Total reaction time at a fixing temperature of 90-98 ° C, 0.1-4 h, preferably 0.2-1.5 h
Total reaction time at a fixing temperature around 25 ° C, 5-40 h, preferably 7-25 h.

3. Continuous process

In this process, piece goods (e.g. cellulose piece goods re) equipped and washed in one operation. The Material comes with the liquor (cyclodextrin derivative, base if necessary salt and additives) impregnated and then dried net. Subsequent treatment at a higher temperature by treatment with hot air or saturated steam or by con clock heat is fixed. Rinse and wash the material  ends the finishing process. Heat fixers are preferred like MCT-β-CD.

Reaction parameters for the cold fixers

pH = 9-12, preferably pH = 10-11
Residence time at 18-60 ° C, preferably 20-40 ° C, 1-10 h, preferably 2-8 h before.
Fixation at 90-160 ° C, preferably 100-140 ° C
Fixing time 5-180 s, preferably 10-100 s

Reaction parameters for the heat fixers such as B. MCT-β-CD

pH = 10-13, preferably pH = 11-12
Fixation at 20-100 ° C, preferably 50-98 ° C, for 0.1-4 h, preferably 0.2-1.5 h. The fixing time at a temperature around 25 ° C is 5-40 h, preferably 7-25 h.
Fixation at 100-230 ° C, preferably 140-220 ° C
Fixing time 10-900 s, preferably 16-600 s

In the process according to the invention, solvents are used preferably water or softened water used.

Alkali chlorides, alkali sulfates, ammonium sul fat preferably sodium chloride, sodium sulfate, ammonium sul fat used.

Additions are e.g. B. urea, alginate.

Alkali hydroxide, alkali carbonates, alkali are used as bases hydrogen carbonates, alkali hydrogen phosphates and their mixtures preferably: NaOH, KOH, sodium carbonate, potassium carbon nat, sodium bicarbonate, potassium bicarbonate, di sodium hydrogen phosphate, dipotassium hydrogen phosphate, trina triumphosphate, tripotassium phosphate, mixtures of NaOH and Sodium carbonate or from KOH and potassium carbonate in particular  preferred: sodium carbonate, mixtures of NaOH and sodium carbonate used.

The components mentioned are preferably used in the following proportions:
CD concentration in the liquor (percent by weight) 0.5-70%, preferably 3-50%, particularly preferably 5-30%.

Salt concentration in the liquor (weight percent) 0-30%, preferably 0-20%, particularly preferably 0-10%.

Additional concentration in the liquor (weight percent) 0-30%, particularly preferably 0-20%.

Base concentration in the fleet (weight percent) 0.2-20% particularly preferably 0.5-10%.

Alkaline reinforcement in the fleet when using carbonates as base (weight percent caustic soda) 0.1-3%, especially preferably 0.3-1%.

The be written procedures cyclodextrin preferably covalently in bound to the outside areas. So the cavities are the Cyclodextrins available and therefore all CD typical Applications possible.

The cavity of the cyclodextrin can be varied be used. Some applications for the equipment of textile materials or leather called: - Active substances can be included in the cyclodextrin and be returned in a controlled manner.

The cyclodextrin acts like an adhesion promoter here. Examples of such active ingredients are: biocides, bactericides, insecticides, fungicides, antimicrobial compounds (e.g. for use in hospital hygiene, shoe equipment etc.), herbicides, pheromones, fragrances (e.g. for the scent finishing of textiles ), Flavoring agents, pharmaceutical agents (e.g. for the treatment of plasters, bandages, tissues for medical applications etc.), agents for antistatic or flame retardant treatment, stabilizers (e.g. against UV radiation), filters (e.g. B. against UV radiation), dyes.
- Active ingredients can be stabilized by the inclusion (against light, temperature, oxidation, hydrolysis, evaporation) and released in a controlled manner.

Due to the possibility of cyclodextrins, it is difficult to dissolve in water Completely complex substances also arise completely new Properties of the materials.

So the storage of welding or welding breakdown pro products in the textile material by complexing them Fabrics prevented. It is also easy to clean the corresponding materials connected (exchange of Sweat products against the surfactants in the wash solution). To there is no smell of sweat left on the material after washing back.

By complexing sweat or sweat breakdown products becomes the smell when wearing these textile materials significantly reduced.

In the case of mixed fibers, equipping them with cyclodextrin derive the hydrophilicity and wettability of the fibers and thus increasing the comfort.  

The reactive cyclodextrin derivatives described can be used as Starch substitute e.g. B. used for permanent crease resistance will.

The cyclodextrin bound to textile material or leather Derivative can also act as an adhesion promoter. B. for polymers Substances with lipophilic residues are used. Leave with it textile materials or leather with completely Equip new fabrics comfortably.

The following examples serve to further explain the Invention.

The following methods were used to characterize the cyclodextrin derivatives:
Thin layer chromatogram (DC):
Eluent: acetonitrile / n-butanol / conc. Ammonia / water = 5/2/1/4.
TLC plates: silica gel, Merck Art. No. 802815.
¹H or 13 C NMR

The DS _Cl value for the nitrogen-containing heterocyclic radicals in the cyclodextrin derivatives of the examples was as follows:
4.5 ml of diethylamine and 4.5 ml of water were added to 1 g of the cyclodextrin derivative according to the invention to be investigated (correspondingly more for samples with a high salt content) in 4.5 ml of water. The solution was at room temp. stirred and then i. Vac. evaporated, mixed with water again and again evaporated to dryness. The residue was then distilled in 20 ml. Water added, 2 d against dist. Water dialyzed (benzoylated cellulose: Sigma Art.

No .: D 7884) and evaporated to dryness again. Possibly. before any precipitate is filtered off. It does not contain Cyclodextrin.

The average degree of substitution (DS _Cl ) per anhydroglucose of active chlorine can then be determined by ¹H-NNR (d6-DMSO / trifluoroacetic acid). It results from the following formula:

DS _Cl = (1/6 _* I1) / ((I2 - 2/3 _* I1) / 7)

mean:
I1 = integral of the methyl protons of diethylamine from 0.5-1.75 ppm, I2 = total integral of all protons of the anhydroglucose of the cyclodextrin derivative and methylene protons of diethylamine from 2.75-6 ppm.

The determination of the DS values for the others may still be in the Residues present derivatives were carried out as known from the prior art.

For the characterization of the cyclodextrin polymers were also used used the following methods:

IR spectroscopy

Measurement of the bleaching of an alkaline phenolphthalein solution (1N NaOH)
Measurement: DC scan in reflection at 572 nm

example 1 Production of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin (sodium salt) DS _Cl 0.3 by reacting β-cyclodextrin with cyanuric chloride

10 g of water and 10 g of ice were placed in a round bottom flask with 1.2 g of NaOH. Within 30 min. 5.5 g of cyanuric chloride were added in three equal portions with vigorous stirring at a temperature of 0 to 5 ° C. At pH 7 and a temperature of 0-15 ° C, a solution of 10 g of β-cyclodextrin (10% water content), in 10 ml of water and 1.2 g of NaOH was then slowly added dropwise to the suspension with vigorous stirring. After stirring for 1.5 h, a pH of 7 was reached. The still cold suspension was sucked off by means of a frit and the precipitate was discarded. After freeze-drying the filtrate, 13.8 g of the chlorotriazinyl-β-cyclodextrin with an ash content of 25.5% were obtained. The average degree of substitution of active chlorine was DS _Cl = 0.3. The water solubility was over 50% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 2 Preparation of 2-chloro-4-hydroxy-β-cyclodextrin (sodium salt) DS _Cl = 0.4

300 g of water, 0.6 g of Texapon K 12 and 150 g of ice were placed in a 2 l round bottom flask. Thereafter, 118.8 g of cyanuric chloride were added in one portion at 0 ° C. and the mixture was evacuated three times with stirring and vented again. 25.95 g of sodium hydroxide solution, dissolved in 270 g of water, were then added dropwise over the course of 1 hour. The temperature then rose to 3 ° C. The pH of the solution was above pH = 12 at this point. The stirring was continued until the pH had dropped to pH 7-8. Then you gave within 10 minutes. 5.19 g of sodium hydroxide solution dissolved in 150 g of water. The pH was then at pH = 11. Then immediately started at 0-5 ° C with the addition of 108 g of β-cyclodextrin (10% water content), dissolved in 270 g of water with 25.95 g of sodium hydroxide solution. The addition took 1 hour. The pH was then <12. The mixture was stirred until the pH had dropped to pH = 11 and then adjusted to pH = 8-8.5 with approximately 20 ml of 0.8% phosphoric acid and suctioned off at 0-5 ° C. via a frit. The precipitate was discarded, the filtrate freeze-dried. This gave the desired cyclodextrin derivative with DS _Cl = 0.4 and an ash content of 32%.

Example 3 Preparation of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin (sodium salt) DS _Cl 0.9

39.6 g of cyanuric chloride were placed under vigorous stirring in 150 g of water at 2 ° C. Then 8.65 g of NaOH in 28 g of water were added within 15 minutes. at 2-3 ° C internal temp. dripped. After the end of dosing, the pH of the suspension was pH = 10-11. Then 36 g of β-cyclodextrin (10% Wasserge content) - dissolved in 54 g of water with 8.65 g of NaOH - within 40 min. added at 5-7 ° C. After the addition, the mixture was stirred at 7 ° C. for a further 25 min, the pH slowly falling to pH = 9-0. After filtration through a glass frit, the powdery precipitate was discarded and the filtrate, which had a pH = 7, was freeze-dried. This gave 67 g of the triazine nyl-β-cyclodextrin derivative with 32% ash content (g / g) and a DS _Cl value of 0.9.

Example 4 Production of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin (sodium salt) DS _Cl 1.5 by reacting β-cyclodextrin with cyanuric chloride

20 g of water and 20 g of ice were initially charged with 3.6 g of NaOH. Then within 45 min. at T = 0-5 ° C 16.5 g of cyanuric chloride are added in four portions. At pH = 7, 10 g of β-cyclodextrin (90%) - dissolved in 30 ml of water with 3.6 g of NaOH - were then slowly added dropwise to the suspension at T = 0-15 ° C. After 2 h a pH = 7 was reached. The still cold suspension was suction filtered and the precipitate was discarded. After freeze-drying the filtrate, 17.54 g of chlorotriazinyl-β-cyclodextrin with a salt content of 44% were obtained. The average degree of substitution of active chlorine was DS _Cl = 1.5. The water solubility was over 25% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 5 Production of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin, (Na salt) DS _Cl 0.5 by reacting β-cyclodextrin with cyanuric chloride

In a 63 liter kettle with an enamel coating, 10 kg of water were cooled to 1 ° C. and 8.6 kg of ice were added. After adding 10 g of sodium dodecyl sulfate as an emulsifier, 2 kg of cyanuric chloride were added to the well-stirred solution. A solution of 0.868 kg of sodium hydroxide in 4 kg of water was then added dropwise at a temperature of 0-5 ° C. in the course of 5 h. The pH should be below pH = 12 during this time. After the alkali had been added, the reaction solution was stirred at 5 ° C. for a further 0.5 h. This gave a clear solution of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine in water. A mixture of 3.08 kg of β-cyclodextrin, 0.434 kg of sodium hydroxide and 4 kg of water was then added dropwise to this well-stirred solution at 5-15 ° C. in the course of 2 hours. During this addition, the pH should be between pH = 10 and pH = 13. The mixture was stirred for a further 1-2 hours until no further change in pH occurred. The pH was then 9.6. The solution came to room temperature. It was then filtered through a 0.45 / 0.2 µm filter. After spray drying the solution (inlet temperature = 235 ° C, outlet temperature = 120 ° C), 5.4 kg of the triazinyl-β-cyclodextrin derivative were obtained with an ash content of 22%. The average degree of substitution of active chlorine was DS _Cl = 0.52. The water solubility was over 55% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 6 Production of 2-chloro-4-hydroxy-triazinyl-β cyclodextrin, (Na salt) DS _Cl 0.5 by reacting β-cyclodextrin with the sodium salt of 2,4-dichloro-6-hydroxy-1,3 , 5-triazine

25 kg of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine as an 8% solution in water were placed in a 63 liter kettle with an enamel coating, and the mixture was stirred at 10 ° C. cooled down. A (cooled) solution of 3 kg of β-cyclodextrin and 0.426 kg of sodium hydroxide in 4 kg of water was then added dropwise to the well-stirred solution within 2 h at 10-15 ° C. During the dropwise addition, the pH was pH = 10-13. After the addition of the β-CD solution, the reaction mixture was stirred for a further 2 hours without cooling until there was no further change in pH. The solution came to room temperature. The solution was then filtered through a 0.45 / 0.2 µm filter. After spray-drying the solution (inlet temperature = 235 ° C., outlet temperature = 120 ° C.), 5.5 kg of the triazinyl-β-cyclodextrin derivative with an ash content of 22% were obtained. The average degree of substitution of active chlorine was DS _Cl = 0.5. The water solubility was over 55% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 7 2-Chloro-4-hydroxy-triazinyl-γ-cyclodextrin (sodium salt) DS _Cl 0.9 by reacting γ-cyclodextrin with cyanuric chloride

20 g of water and 10 g of ice were initially charged with 2.4 g of NaOH. Then within 30 min. at T = 0-5 ° C, 11 g of cyanuric chloride are added in three portions and the mixture is stirred at 5 ° C until a pH = 7 has been reached. 1.2 g of NaOH were added to the suspension. Then 10 g of γ-cyclodextrin (dissolved in 20 ml of water with 1.2 g of NaOH) were slowly added to the suspension at T = 0-15 ° C. After 1.5 h a pH = 7 was reached. The still cold suspension was suction filtered and the precipitate was discarded. After freeze-drying the filtrate, 20.9 g of chlorotriazinyl-γ-cyclodextrin with an ash content of 33% (g / g) were obtained. The average degree of substitution of active chlorine was DS _Cl = 0.9, the water solubility was 25% (g / g). Γ-Cyclodextrin was no longer detectable in the thin-layer chromatogram.

Example 8 Chlorotriazinyl-β-hydoxypropylcyclodextrin MS (hydroxypropyl) 0.77, DS _Cl 0.7 by reacting hydroxypropyl-β-cyclodextrin with cyanuric chloride

20 g of water and 10 g of ice were initially charged with 2.4 g of NaOH. Then within 30 min. at T = 0-5 ° C 11 g of cyanuric chloride added in four portions. At pH = 7, 10 g of HP-β-cyclodextrin MS 0.77 - dissolved in 20 ml of water with 2.4 g of NaOH - were then slowly added dropwise to the suspension at T = 0-15 ° C. After 1.5 h a pH = 7 was reached. The still cold suspension was suction filtered and the precipitate was discarded. After filtration and freeze-drying of the filtrate, 21.4 g of the chlorotriazinyl-β-hydroxypropyl-cyclodex trine derivative were obtained. The solubility in water was 25% (g / g), the ash content was 33% (g / g). The average active chlorine content per anhydroglucose unit was DS _Cl = 0.7.

Example 9 Production of dichlorotriazinyl-β-cyclodextrin DS _Cl 1.0 by reacting β-cyclodextrin with cyanuric chloride

9.1 g of β-cyclodextrin and 2 g of NaOH were placed in 26 g of water. 7.36 g of cyanuric chloride were added in 3 portions at 2 ° C. within 30 minutes and the mixture was stirred. After 2 h the pH was 7.2. The pH was stabilized by adding 4 g Na₂HPO₄ and 6 g KH₂PO₄ in 50 g water. The solution was filtered cold and then freeze-dried. 19.6 g of the dichlorotriazinyl-cyclodextrin derivative with 39% ash content were obtained. The DS _Cl of active chlorine was 1.0.

Example 10 Implementation of 3-N-ethylamino-2-hydroxypropyl-β- Cyclodextrin (MS 0.17) with cyanuric chloride (attachment of the Cyclodextrins to the heterocycle via a spacer)

3-N-ethylamino-2-hydroxypropyl-β-cyclodextrin (MS 0, 17) was de using the method of A. Deratani and B. Pöpping (Macro mol. Chem., Rap. Commun. 13, 237-41 (1992)) by implementation of 3-chloro-2-hydroxypropyl-β-cyclodextrin with ethylamine manufactured.

1.1 g of cyanuric chloride were placed in 5 g of water, 5 g of ice and 0.24 g of NaOH at a temperature of 0 to 5 ° C. The suspension was stirred until a pH of pH = 7 was reached. Thereafter, 1 g of the basic β-cyclodextrin derivative (3-N-ethylamino-2-hydroxypropyl-β-cyclodextrin (MS 0.17)) dissolved in 5 g of water was added dropwise. The mixture was stirred at T <5 ° C for 5 hours. By adding 4 ml of 10% NaHCO₃ solution (g / g), the pH was adjusted to 6.9 and the suspension was filtered. Freeze drying gave 1.6 g of the desired cyclodextrin derivative with a salt content of 42% (g / g). The average active chlorine content per anhydroglucose was DS _Cl = 0.1.

Example 11 Implementation of hydroxypropyl-β-cyclodextrin (MS 0.9) with 2,4,5,6-tetrachloropyrimidine

12 g of hydroxypropyl-β-cyclodextrin (MS 0.9) were dissolved in 30 g of water. 8.72 g of 2,4,5,6-tetrachloropyrimidine, dissolved in 30 ml of acetone, were then added dropwise with vigorous stirring at 30-35 ° C. and a pH of pH = 6-6.5 within 1 h. The pH was kept constant with an aqueous sodium hydroxide solution. After addition of the pyrimidine, stirring was continued for 1 h, the acetone was evaporated off, filtered and the filtrate was freeze-dried. 5 g of the reactive component according to the invention were obtained with a salt content of 31% and an active chlorine content of DS _Cl = 0.5.

Example 12 Production of basic cyclodextrin derivatives by reacting monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (Example 2) with diethylamine

1.6 g of the monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4 (in game 2) were dissolved in 10 ml of water and mixed with 5 ml of diethylamine, 20 h at room temperature. stirred and then i. Vac. evaporated, mixed with water again and again evaporated to dryness. Then the residue was distilled in dist. Water added and 2 d against dist. Water dialyzed. The precipitate formed was filtered off (according to 13 C-NMR it contains no cyclodextrin). The solution was then evaporated to dryness. 1.6 g of the basic cyclodextrin derivative were thus obtained.

Example 13 Production of basic cyclodextrin derivatives by reacting monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with ethylamine

The reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (example 2) with ethylamine was carried out as described in example 10. 0.8 g of the amine derivative was obtained from 1 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4.

Example 14 Preparation of dihydroxy-triazinyl-β-cyclodex trin

15 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (Example 2) were heated to 70 ° C. in 1 l of water. The pH value dropped to pH = 3.9. Within 1 h, the solution was mixed with 3.3 g of NaOH - dissolved in 22 ml of water - and kept at 70 ° C. for two more hours. The pH was then adjusted to 7 with 2N HCl. The solution was then concentrated to 80 ml on a rotary evaporator.

This solution was then used over a period of 60 min. dropped in 720 ml of methanol. The precipitation was with Washed 90% methanol. 7.5 g of dihydroxy-triazi were obtained nyl-β-cyclodextrin with a sodium chloride content of 5.8%.

Example 15 Reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with triethylamine to produce charged cyclodextrin derivatives

15 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 prepared according to Example 2 were dissolved in 60 ml of water and mixed with 30 ml of triethylamine. The clear solution was stirred at 60 ° C. for 24 h. For working up, the mixture was evaporated in vacuo, the residue in dist. Water absorbed and against dist. Dialyzed water 2 d. After freeze-drying, 19 g of the loaded cyclodextrin derivative were obtained. The average degree of substitution of triethylamine per anhydroglucose was 0.3. This derivative can also be used as a reactive component with triethylamine as a leaving group.

Example 16 Production of a water-insoluble Cyclodex trinoligomers by reaction of monochlorotriazinyl-β- Cyclodextrin with itself

7.5 g of monochlorotriazinyl-β-cyclodextrin prepared according to Example 2 was mixed with 2.5 g of sodium carbonate, in a grater well mixed and overnight at 80 ° C stored. There was an insoluble cyclodextrin polymer which is powdered in a mortar and thoroughly poured into 1 liter of water stirs and was sucked off over a frit. You got that 4.5 g of the insoluble cyclodextrin polymer.

Example 17 Production of a modified with cyclodextrin ten polyallylamine by reacting monochlorotriazinyl-β- Cyclodextrin with polyallylamine

5 g of polyallylamine (PAA, commercially available, for example, from Aldrich, Steinheim, under order number 28.321-5) were dissolved in 25 g of water. The pH of the solution was adjusted to pH = 7 with NaOH. The solution was mixed with 0.1 g Na₂CO₃ and heated to 40 ° C. Thereafter, 1.7 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) were prepared analogously to Example 2. The solution obtained was heated to 98 ° C. in 45 min and a further 0.3 g of Na₂CO₃ were added and kept at that temperature for an hour. The pH was then 6.6. A blank with β-cyclodextrin instead of the tri azinyl derivative was used as a comparison. Here the pH at the end of the reaction was pH = 9.7. For working up, the mixture was adjusted to pH 7 with NaOH and 5 d against dist. Water dialyzed (dialysis tubing available, for example, from Sigma, Deisenhofen, under the order number Sigma D 9652) and then freeze-dried. The incorporation of the triazinyl derivative was demonstrated using the IR spectrum (KBr pellet). An insoluble polymer was formed from the soluble PAA.

Example 18 Representation of a modified with cyclodextrin ten polyvinyl alcohol by reacting monochlorotriazi nyl-β-cyclodextrin with polyvinyl alcohol

The reaction was carried out as described in Example 17, respectively but with polyvinyl alcohol (available for example from Wacker-Chemie, Munich, under the name Wacker V03 / 180) as a soluble polymer. The pH was at the end of the Reaction at pH 7.7. A soluble polymer was obtained The incorporation of the triazinyl derivative was carried out by 13 C-NMR proven.

Example 19 Representation of a modified with cyclodextrin starch by reacting monochlorotriazinyl-β-cyclo dextrin with starch

5 g of starch (available, for example, from Merck under item number Merck 1252.0250) were dissolved in water at 98 ° C. and cooled. At 40 ° C, 0.1 g of Na₂CO₃ and 1.7 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) were prepared analogously to Example 2. Within 45 minutes. was heated to 98 ° C. The solution was then mixed with 0.3 g Na₂CO₃ and hold ge at 98 ° C for 1 h.

A solid with a rubber-like consistency was formed. To Add 25 ml of water and cool to room temperature one held rubber-like crumbs, which separated and 5 d against least Water were dialyzed (Sigma D 9652). The installation of the triazine derivative could be verified by an IR spectrum will be. The product obtained was insoluble in water Lich polymer.

Example 20 Production of a modified with cyclodextrin cellulose

1.7 g monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) prepared analogously to Example 2 were placed in 25 g water, the solution was mixed with 0.1 g Na₂CO₃ and stirred briefly at 40 ° C. This was followed by the addition of 5 g of cellulose (available, for example, from Fluka under order number 22183). Within 45 min. the solution was heated to 98 ° C, after 15 min. or 30 min. 0.5 g of sodium chloride were added in each case. At 98 ° C, 0.3 g of Na₂CO₃ was added. The solution was kept at 98 ° C for 1 h. The mixture was then cooled to room temperature, the modified cellulose was filtered off with suction and washed thoroughly with water. The cellulose was then 5 d against dest. Water dialyzed (Sigma D 9652). The incorporation of the triazinyl derivative was demonstrated on the basis of the IR spectrum. A cellulose treated in boiling water for 2 hours and a cellulose treated as described above but without addition of the triazinyl derivative served as a comparison.

Example 21 Reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with cotton

Monochlorotriazinyl-β-cyclodextrins can be as in fol gend described slightly with soda at 90-98 ° C analog commonly gene coloring techniques of monochlorotriazine reactive dyes apply to cotton. The cotton (Style 407 and 467) was obtained from Testfabrics, Inc. (P.O. Box 420/200, Blackford Avenue, Middlesex, N.J. 08846-0420, USA).

20 g of cotton were prepared in a solution of 8 g of monochlorotriazonyl-β-cyclodextrin DS _Cl 0.4 (40% ash) prepared analogously to Example 2 and 0.5 g of soda in 100 ml of water and within 45 minutes. heated to 98 ° C. After 15 minutes each time. each 2.5 g of sodium chloride to the solution. A further 1.5 g of soda were added at 98.degree. It was fixed at this temperature for 1 h. The fabric was removed from the bath and washed thoroughly with water. By measuring the bleaching of an alkaline phenolphthalein solution, it was demonstrated that cyclodextrin was covalently bound to the cotton.

Cyclodextrin decolorizes alkaline phenolphthalein solution (see hey B. J. Chem. Soc. Perkin Trans. 2 1992). The Beschich tion of the cotton with cyclodextrin can consequently via the Fading of an alkaline phenolphthalein solution (solution in 1 N NaOH). The quantification took place by a DC scanner at 572 nm in reflection position (Device: Desaga, chromatogram densitometer CD 50) after the dye in different concentrations on the treated cotton had been applied. As comparison served the untreated cotton, as well as cotton,  which have been treated analogously to the procedure described above but with β-cyclodextrin instead of the triazinyl deri vates.

Example 22 Reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with filter paper

Several filter papers (30 × 10 cm) were prepared with a solution of 2.6 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) analogously to Example 2 and 0.63 g of sodium carbonate in 50 ml of water and at Dried 80 ° C overnight in a drying cabinet. The papers were then washed 3 times with 1.5 l of water for 3 h each. As a comparison, another filter paper was soaked with the above solution without a triazine derivative and treated identically.

The paper coated with the cyclodextrin derivative was much smoother and firmer than the untreated one. The Treated papers decolorized alkaline phenolphthalein solution much stronger than the untreated. That at the So surface bound cyclodextrin derivative was still in able to complex phenolphthalein.

Example 23 Storage stability of monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4

5 g of the monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4 (example 2) were in 50 ml 0.25 M phosphate buffer with different pH values, in dist. Water as well as in dist. What water, which had been adjusted to pH = 1 or pH = 14 with 2N HCl or 2N NaOH, dissolved. The pH of the solutions and the DS _Cl value of the cyclodextrin derivative were determined over 46 days.

Result

In buffered solutions at pH = 8 this is 2-chloro-4-hydroxy 1,3,5-triazinyl-β-cyclodextrin (sodium salt) in particular stable.

Table 1

pH values

Table 2

DS _Cl values

Example 24 Dialysis of monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4

2 g of the monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4 (example 2) were distilled in 10 ml. Dissolved water and 5 times against 10 l of dist. Water which had previously been adjusted to pH = 8.5 with 2N NaOH was dialyzed. The salt content then dropped to <0.5% (g / g). The DS _Cl value after dialysis was DS _Cl = 0.35.

Example 25 Determination of the incorporation rate of the triazine heterocycle in β-cyclodextrin in the production of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin, (Na salt) DS _Cl 0.5 by reaction of β-cyclodextrin with the sodium Salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine

785 g of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine as an 8% solution in water were placed in a 1 liter round-bottomed flask and cooled to 10 ° C. with stirring. A (cooled) solution of 135.76 g of β-cyclodextrin (dry weight) and 13.4 g of sodium hydroxide in 130 g of water was then added dropwise to the well-stirred solution within 1.5 h at 10-15 ° C. This resulted in a theoretical DS _Cl value of DS _Cl 0.4. The pH was pH 10-13 during the dropping. After the addition of the β-CD solution, the reaction mixture was stirred for a further 4 h without cooling until there was no more pH change. A sample of this reaction mixture was then mixed with diethylamine to determine the DS _Cl value. In this test it was DS _Cl 0.35. This corresponds to an incorporation of the triazine heterocycle in β-cyclodextrin of 87.5%.

Analogously, further experiments were carried out to determine the installation rates for derivatives with different theoretical DS _Cl values. The following table provides information on the results.

Example 26 Equipping a cotton T-shirt with MCT-β-CD 0.5

35 g MCT-β-CD DS 0.438.5 g sodium carbonate
14 g sodium chloride
700 g water
70 g of fabric

MCT-β-CD, sodium carbonate was dissolved in water and the T- Half-immersed shirt. Within 45 min Liquor heated to 98 ° C. After 15 minutes and 30 min 7 g of sodium chloride added. The temperature of 98 ° C was held for 1 h. The T-shirt was removed from the fleet taken, cooled and thoroughly rinsed with water several times and washed cold.

The T-shirt so equipped with MCT-β-CD was on the skin carried. On the one equipped with the cyclodextrin derivative There was significantly less sweat smell on the side of the T-shirt deliver. The t-shirt was worn a total of 4 times at 40 ° C with a normal detergent in the washing machine washed and worn again. The ability of the material Binding sweat odor through complexation was even after the 4th wash cycle is still present. The cyclodextrin derivative consequently had to be covalently linked.  

Example 27 Equipping a cotton T-shirt with MCT-β-CD 0.5

20 g MCT-β-CD DS 0.4
1 g sodium carbonate
4 g sodium chloride
200 g water
109 g of fabric

MCT-β-CD and sodium carbonate were dissolved in 200 ml of water. The damp, well wrung out cotton t-shirt was on finally half immersed in this solution. After it the T-shirt was soaked up with the fleet put a plastic bag and dry at 60 ° C for 4 h cabinet annealed. Then it became thorough several times washed hot and cold with water.

The t-shirt so equipped with MCT-β-CD was worn. Out the side of the T- equipped with the cyclodextrin derivative Shirts had significantly less smell of sweat.

Example 28 Coating of cotton fabric with MCT-β-CD 0.4

• 1) 1.024 g of sodium carbonate was dissolved in 45 ml of water. There after a total of 5 g of MCT-β-CD 0.4 was added (anhydrous) and stir until a clear solution is obtained.
• 2) 1 g of cotton fabric (Style 407, see Example 21) was on closing with constant stirring with the tweezers for 5 min dipped in this prepared solution.
• 3) Then the fabric was placed on a PVC board, approx. 50 × 35 cm, smoothed out and with a VA tube so long under rollers squeezed (the squeezed liquid was always with  a cloth removed) until the weight of the fabric practically no longer changed. With 1 g of substance used and a 10% MCT solution was the weight of the wet 1.5 g.
• 4) The fabric was then circulated at 90-100 ° C for 60 min fixed cabinet.
• 5) This was followed by a washing process. In addition, the fabric fixed with MCT-β-CD for 3 min under flowing hot water water and washed under running cold water for 2 min repeatedly expressed).
• 6) The wet material was now in the Petri dish over one Plastic stoppers placed and at 90 ° C in the drying cabinet 60 min dried.
• 7) The dried fabric was weighed out. The weight gain was 33 mg.
• 8) Then with the dry, coated fabric carried out the hydrocortisone test described in Example 29 leads.

Points 2-6 can be repeated any number of times to increase the occupancy of the substance with MCT-β-CD.

Example 29 Complexation of hydrocortisone by MCT coated cotton fabric A) Preparation of a hydrocortisone stock solution

• 1) 500 ml of demineralized water containing 200 mg were used for the stock solution Hydrocortisone approx. 16 h in a well sealed bottle shaken on the laboratory shaker. Then the approach first filtered through a pleated filter and then through a Sterile filter to separate undissolved fine particles.  
• 2) 450 ml of this clear solution were poured into a 500 ml Volumetric flask filled and made up to the mark with demineralized water fills (= stock solution).
• 3) With the help of HPLC the content of dissolved Hydrocor tison in this stock solution. It was 0.253 mg / ml.

B) Complexation of hydrocortisone by MCT-coated Cotton fabric

• 1) 5 ml of the stock solution with 5 × 0.253 mg = 1.265 mg Hydrocor tison and 5 ml of deionized water were placed in a 30 ml wide-mouth bottle pipetted with a measuring pipette. 1.033 g with MCT-β-CD coated, dry fabric from Example 28 was folded and pressed into the solution with a spatula so that the fabric was soaked well.
• 2) The mixture was then shaken on a laboratory shaker at RT for 18 h telt.
• 3) The liquid was poured into a 50 ml Volumetric flask decanted, the material carefully with the tweezers pulled into the funnel and well poured with a pestle presses.
• 4) The fabric was then washed in a beaker . To do this, he was using tweezers in 5 ml of deionized water then presses into an ultrasonic bath for 5 min poses.
• 5) The wash water was again dean in the volumetric flask animal, carefully pull the fabric out of the beaker and with the pestle in a funnel again over the measuring cylinder pressed out.
• 6) The volumetric flask was then Replenished water.
• 7) The HPLC content was not complexed hydrocortisone in the solution.  
• 8) In parallel, 1 g of an uncoated substance was used as Control treated the same.

Result

During the hydrocortisone content in the volumetric flask when checking test with untreated cotton fabric unchanged at 1.3 mg, it sank after immersing the treated fabric fes to 0.77 mg. This showed that the Kavi Cyclodextrin also after binding to cotton was still available.

Example 30 Coating of cotton fabric with MCT-β-CD 0.4

• 1) 1 g of cotton fabric (Style 407, see Example 21) was analogous to Example 28 with MCT-β-CD 0.4 by single thawing Chen in 10% MCT-β-CD occupied (1st occupancy). Then was de the hydrocortisone test was carried out.
• 2) The fabric was washed in a washing machine in a 70 ° C Wash program with a common detergent and rinsed.
• 3) The hydrocortisone test was then carried out analogously Example 29 performed.
• 4) Points 2) and 3) were repeated again.
• 5) After the third wash, the cotton fabric was again analogous to point 1) with MCT-β-CD. Then were points 2), 3) and 4) are repeated.
• 6) Again after the third wash the cotton fabric load again with MCT-β-CD as described in point 1). Subsequently points 2), 3) and 4) were repeated.
• 7) In parallel, 1 g of an uncoated substance was used as Control treated the same.

The following table summarizes the results:

Result

This experiment showed that the equipment stung of the substance with MCT-β-CD is washable and that covalently bound cyclodextrin again and again can be loaded onto a guest.

Example 31 Application of the Frescolat ML fragrance a cotton fabric coated with MCT

• 1) 1 g of cotton fabric (Style 407, see Example 21) was coated with 5.5% MCT-β-CD. The substance became analogous to this Example 28 in a 20% aqueous MCT-β-CD 0.4 solution dives, dehumidifies, fixes, washed and dried.
• 2) The coated fabric was now in on a watch glass put an exicator. A crystalli was placed next to it sier bowl with 10 ml water and a second watch glass with 250 mg Frescolat ML.
• 3) The desicator was closed and in for 16 h at 50 ° C put a drying cabinet.
• 4) Then the desicator was allowed to come to room temperature, took out the slightly damp cloth and dried it Room temperature.
• 5) The fabric was then baked at 100 ° C to to remove uncomplexed Frescolat ML.

Result

The dry cotton fabric has no smell. He will however slightly moistened, the herbal is immediately emphasized minty note of the ML Frescolate clearly recognizable.  

• 6) To quantify the content of Frescolat ML, the material was covered in a flask with 110 ml of water and a total of 150 min with a liquid / liquid extraction Subjected to 50 ml of hexane for a total of 150 min.
• 7) The cooled hexane phase was placed in a 100 ml volumetric flask ben transferred and filled up to the mark with hexane. On the Frescolat ML content was then determined via gas chromatography.

Result

A total of 2.834 mg of Frescolat ML were complete on the fabric xiert.

Example 32 Application of the Frescolat ML fragrance a cotton fabric coated with MCT

• 1) 1 g of cotton fabric (Style 407, see Example 21) was coated with 5.5% MCT-β-CD. The substance became analogous Example 28 in a 20% aqueous MCT-β-CD 0.4 solution dives, dehumidifies, fixes, washed and dried.
• 2) The coated fabric was now immersed in water and well pressed. The only slightly damp material was on finally placed in a desicator. In addition, one hired second watch glass with 250 mg Frescolat ML.
• 3) The desicator was closed and in for 16 h at 50 ° C put a drying cabinet.
• 4) Then the desicator was allowed to come to room temperature, took out the slightly damp cloth and dried it Room temperature.
• 5) The fabric was then baked at 100 ° C to to remove uncomplexed Frescolat ML.

Result

The dry cotton fabric has no smell. He will however slightly moistened, the herbal is immediately emphasized minty note of the ML Frescolate clearly recognizable.

• 6) To quantify the content of Frescolat ML, the material was covered in a flask with 110 ml of water and a total of 150 min with a liquid / liquid extraction Subjected to 50 ml of hexane for a total of 150 min.
• 7) The cooled hexane phase was placed in a 100 ml volumetric flask ben transferred and filled up to the mark with hexane. On the Frescolat ML content was then determined via gas chromatography.

Result

A total of 3.481 mg of Frescolat ML were complete on the fabric xiert.

Claims (6)

1. Textile material or leather, characterized in that it is equipped with 0.1 to 25 wt.% At least one reactive cyclodextrin derivative with at least one nitrogen-containing heterocycle. 2. Material according to claim 1, characterized in that it with 0.3 to 10% by weight of at least one reactive Cyclodextrin derivative with at least one nitrogen equipped heterocycle. 3. A method for producing the materials according to claim 1 or 2, characterized in that reactive Cyclodex trine derivatives, in a suitable reaction medium (flot te) with the addition of bases and possibly salts and additives sets to the reaction medium dissolved, in the neutral to basic milieu applied to the materials or leather brings, the materials or the leather dried if necessary and then fixed at temperatures of 20-220 ° C. will. 4. The method according to claim 3, characterized in that reactive cyclodextrin derivatives are used, the nitrogen-containing heterocycle one to three electrophilic Centers. 5. The method according to claim 4, characterized in that the electrophilic centers are the same or different and are carbon atoms on which halogen, in particular re F, Cl, or an ammonium substituent, in particular Trialkylammonium or a substituted or unsubsti tuiert Pyridinium substituent, is covalently bound.   6. The method according to claim 3, characterized in that reactive cyclodextrin derivatives of the following formula I: where R is OH or OR¹ or R² and
R¹ is a hydrophilic residue which may be the same or different and
R² is a nitrogen-containing heterocycle which is either directly attached or is attached via a spacer by means of an ether, thioether, ester or amine bond,
wherein the spacer is an alkyl or hydroxyalkyl radical with 1-12 carbon atoms which is bonded to the anhydroglucose via an ether, thioether, ester or amine bond and
the nitrogen-containing heterocycle comprises at least one halogen or one ammonium substituent and is present at least once per cyclodextrin and
n means 6, 7 or 8
be used.