DE19858734A1 - Non-felting wool for production of textiles is obtained by plasma pretreatment and optional treatment with aqueous dispersion of self-dispersing isocyanate, followed by treatment with softener and non-slip finish - Google Patents

Abstract

Non-felting wool is obtained by (a) pretreatment with plasma and (b) optional treatment with an aqueous dispersion of self-dispersing isocyanate, followed by treatment with (c) a softener and then (d) a non-slip finish. An Independent claim is also included for the process as described above.

Description

The invention relates to felt-free finished wool and a method for felt-free armor by treating the wool with a plasma and then a Aftertreatment with various finishing agents.

In the textile processing industry there is a particular interest in a ver reduction in the tendency to felt of wool, in particular raw wool or un processed wool. Usually the matting of the wool is done by finishing reduced with special aids.

For a long time, isocyanates have been used as auxiliaries for the finishing of textiles knows and can, as described for example in DE-OS-19 04 802, in organic solvents are used, or, as in DE-OS-17 69 121 be wrote, in aqueous dispersion with the addition of emulsifiers. Both organic Solvents and optionally wastewater-polluting emulsifiers are today out of date for ecological and industrial hygiene reasons. Ent Therefore self-dispersing isocyanates as well as formulations were developed with the smallest possible amounts of solvents or emulsifiers as auxiliaries and Additives.

DE-OS-17 94 221 describes the treatment of fiber materials with isocyanate Prepolymers that still contain free isocyanate groups; this equipment can be in Solvents such as perchlorethylene or in aqueous emulsion using Auxiliary emulsifiers are used.

US-A-3,847,543 discloses a method for non-felting of wool in which in aqueous dispersion at the same time aliphatic isocyanates, OH-functional Ver network and organometallic catalysts are present. Although this ver  drive in the aqueous phase, auxiliary solvents and emulsifiers are required Lich.

DE-OS-26 57 513 describes a process for the felt-free finishing of wool the wool yarn is treated with an aqueous liquor which contains a felt-free agent holds. Reactive polyolefins, reaction products made of poly isocyanates and hydroxy compounds, silicone polymers, aziridine compounds, Reaction products of epoxides with fatty amines and dicarboxylic acids or poly amides, reaction products with thiosulfate end groups or preferably Um Settlement products with mercapto end groups used.

WO 95/30045 describes a process in which special isocyanates are used to free felt armor of wool can be used. Here can be solvent-free and without an emulsifier be worked because the isocyanates used are water dispersible. To next, the wool is subjected to a pretreatment using oxidizing agents, followed by a reduction treatment before the water-dispersing isocy anate are used.

Another prior art method for the non-felting of Wool described in which the wool is treated with a plasma. From the DE OS-43 44 428, for example, a method is known in which the wool to felt free equipment of a combination of plasma or corona pretreatment and is subjected to enzymatic aftertreatment. Here the wool is in front of the Enzyme treatment with a solution containing sulfide ions sensitized.

DE 196 16 776 C1 also describes a method for finishing felt-free wool, in which moist wool material with a water content of 4-40% by weight is subjected to a low-pressure plasma treatment prior to further processing into textile fabrics or webs. At a pressure of 10 ^-2 -10 mbar, the wool is exposed to a high-frequency discharge of a frequency of 1 kHz-3 GHz and a power density of 0.001-3 W / cm ³ over a period of 1-600 seconds, optionally with the addition of non-polymerizing Gases.

From the unpublished German patent application with the file number 197 36 542.6 is also known a process for the felt-free finishing of wool, at to which the wool is also initially exposed to a low-pressure plasma finally with aqueous dispersions of self-dispersing isocyanates will act.

All of the above methods for felt-free finishing of wool have the ge common disadvantage that the application of funds for felt-free finishing the grip properties of the wool deteriorate. One is often observed straw-like feel of the treated wool materials.

The object of the present invention was therefore to provide wool to provide, on the one hand, a felt-free equipment, d. H. after further processing Work on made-up goods in machine wash not or only very much slightly matted or shrunk, and on the other hand improved handles features.

The present invention is felt-free finished wool, characterized in that the wool

• a) is exposed to plasma in a pretreatment,
• b) optionally self-dispersing with an aqueous dispersion Isocyanate is treated
• c) then with a plasticizer as well
• d) finally treated with an anti-slip agent, if necessary.

The present invention also relates to the method for armoring wool felt-free, characterized in that the wool

• a) is exposed to plasma in a pretreatment,
• b) optionally self-dispersing with an aqueous dispersion Isocyanate is treated
• c) then with a plasticizer as well
• d) finally treated with an anti-slip agent, if necessary.

The plasma treatment of the wool according to step a) of the ver driving can either in the form of a low-temperature plasma treatment at ver reduced pressure or in the form of a corona treatment.

The wool used can be a wide variety of wool materials act, e.g. B. raw wool after raw wool washing, dyed or undyed wool sliver, dyed or undyed woolen yarn, knitted fabric, knitted fabric or fabric. The water content of the wool is usually 4 to 40% by weight, preferably 5 to 30% by weight, particularly preferably 6 to 25% by weight and in particular 8 to 15 % By weight.

The low-temperature plasma treatment is described in detail in DE 196 16 776 C1, to which reference is hereby expressly made. The wool is subjected to a high-frequency discharge with a frequency of 1 kHz-3 GHz and a power density of 0.001-3 W / cm ³ at a pressure of 10 ^-2 -10 mbar over a period of 1-600 seconds, optionally with the addition of non-polymerizing gases.

It is preferably carried out under a pressure of 0.1-1 mbar and above a period of 2-5 minutes.

The actual low-temperature plasma is generated by feeding in electromagnetic radiation in the frequency range from 1 kHz to 3 GHz. In a preferred variant, the low-temperature plasma is generated via a microwave discharge of 1-3 GHz (the power density at the decoupling is in particular 0.1-15 W / cm ² ). The electromagnetic radiation can be supplied continuously or pulsed. A pulsed high-frequency discharge with a pulse frequency of up to 10 kHz has proven particularly useful.

In the case of additional use of non-polymerizing gases as Plasma process gases are fed into the system at a flow rate of up to 200 l / h Plasma treatment room embedded. In particular, non-polymerizing gases are special oxygen, nitrogen, noble gases, especially argon, air or mixtures of these gases.

Construction and apparatus arrangements of a low-temperature plasma reactor are known per se. An electrodeless reactor with a coupling for microwaves is preferably used. The wool to be treated is preferably placed below the decoupling unit. The distance between the wool and the coupling unit is preferably 1-30 cm, in particular 2-10 cm. After the wool to be treated has been introduced into the reactor, it is suitably evacuated with vacuum pumps so that the pressure during the plasma treatment is in the range from 10 ^-2 -10 mbar, preferably from 0.1-1 mbar. In continuous continuous operation, special vacuum locks are preferred, which enable the material to be fed in and out without flow.

As an alternative to this embodiment of the low-temperature plasma treatment under low pressure, the wool can also undergo a corona treatment at a pressure in the Range of 100 mbar-1.5 bar, preferably at normal pressure. The Corona treatment is detailed in a German submitted on the same day Patent application described.

In the corona treatment, the wool is subjected to a high-frequency discharge with a power density of usually 0.01-5 Ws / cm ² over a period of 1-60 seconds, preferably 2-40 seconds and in particular 3-30 seconds, optionally with the addition of non-polymerizing Gases. Suitable non-polymerizing gases are air, oxygen, nitrogen, noble gases or mixtures thereof.

The actual plasma is generated by applying an alternating voltage of 1-20 kV Frequency range between 1 kHz and 1 GHz, preferably 1-100 kHz at electrodes testifies, wherein one or both poles are provided with an insulator material. The AC voltage can either be continuous or with individual pulses or with pulse trains and breaks in between.

Construction and apparatus arrangements of a corona reactor are in themselves knows and for example in the unpublished German application with the file number 197 31 562. Corona treatment is preferred performed on electrical discharges in the normal pressure range by the to be acting wool first inserted into a closed, sealed treatment housing leads there with the working gas, d. H. the non-polymerizing mentioned above Gas, loaded and then in a gap between at least two Be electrodes is exposed to an electrical barrier discharge. The Ab level of the wool material to the treatment electrodes is 0-15 mm, preferred 0.1-5 mm and especially 0.3-2 mm. The treatment electrodes are preferred formed as rotatable rollers, one or both of which are electrically fixed dielectric material are coated.

Carrying out the corona treatment at a pressure in the range from 100 mbar to 1.5 bar, preferably at normal pressure, has the advantage in comparison to the low-pressure plasma treatment at 10 ^-2 -10 mbar that the apparatus arrangement is much less complex than at Low pressure treatment. No vacuum pumps are required and there is no need to install special vacuum locks.

The special effect of the plasma treatment in step a) of the invention Procedure could be explained as follows. The liquid present in the fiber desorbs as water vapor / gas from the fiber surface during the process. It comes to the formation of high-energy electrons, ions and highly excited neutral molecules or radicals that act on the surface of the fiber, the water vapor desorbed from the fiber causes immediate Particularly reactive particles are formed near the respective fiber surface, that act on the surface.

After the plasma treatment of the wool in step a), a post-treatment with various finishing agents is carried out. Optional step b) involves treating the wool with an aqueous dispersion of self-dispersing isocyanates. The self-dispersing isocyanates that can be used are the subject of the unpublished German patent application with the file number 197 36 542.6. They have an isocyanate content of 1-25% by weight, calculated as NCO (with a molecular weight of 42 g / mol), and can be obtained by reaction in any order from:

• A) organic polyisocyanates with an average NCO functionality of 1.8-4.2 with
• B) polyalkylene oxide alcohols, amines and / or thiols of the formula 1,
  R ¹ R ² N- (CHX-CHY-O) _n -CHX-CHY-ZH (1)
  in which
  n represents a number from 3-70,
  X and Y are hydrogen or methyl, where in the event that one of the radicals X or Y is methyl, the other must be hydrogen,
  R ¹ and R ² independently of one another are straight-chain or branched C ₁ -C ₆ -alkyl radicals or straight-chain or branched C ₁ -C ₆ -acyl radicals, in the case where R ^{1 is} a straight-chain or branched C ₁ -C ₆ -acyl radical , R ^{2 can} also be hydrogen, and furthermore R ¹ and R ² together can also form a - (CH ₂ ) _m - alkylene radical with m = 4, 5, 6 or 7, in which one or two CH ₂ groups are represented by O and / or NH can be replaced and / or one or two CH ₂ groups can be substituted by methyl, and Z represents O, S or NH,
  and if necessary
• C) further NCO-reactive compounds which contain anionic, cationic and / or potentially anionic or cationic groups,
  and if necessary
• D) other auxiliaries and additives.

The term "self-dispersing" in the present context means that the Isocyanates in a concentration of up to 70% by weight, preferably up to 50 % By weight, finely divided dispersions in water with particle sizes of <500 nm give (measured using an ultracentrifuge).

The following compounds are suitable for producing the self-dispersing isocyanates:

• A) Unmodified (ie not previously reacted with OH-functional compounds), aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanates with an average NCO functionality of 1.8-4.2. Before are given aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanates which have uretdione and / or isocyanurate and / or allophanate and / or biuret and / or oxadiazine structures and which in a manner known per se from aliphatic, cyclo aliphatic, araliphatic or aromatic diisocyanates can be produced.
  Examples of aliphatic or cycloaliphatic diisocyanates are 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl 1,6-diisocyanatohexane, 1,3- and 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl cyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethyl-cyclohexane, 4,4-Di isocyanato-dicyclohexylmethane or any mixtures of the aforementioned diisocyanates are suitable.
  Examples of suitable aromatic diisocyanates are tolylene diisocyanate, 1,5-diisocyanatonaphthalene and diphenylmethane diisocyanate.
  The preferred polyisocyanates having uretdione and / or isocyanurate and / or allophanate and / or biuret and / or oxadiazine structures and having an average NCO content of 19-24% by weight are essentially the trimers Reaction products of 1,6-diiso cyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclo hexane and the corresponding higher homologues.
  Most preferably, uretdione group-free, iso cyanurate group-containing polyisocyanates of the stated average NCO content are used. They can be obtained by known catalytic trimerization of 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane with formation of isocyanurate and preferably have an average NCO functionality of 3.2 -4.2 on. Also preferred are the trimeric polyisocyanates obtained by reaction of 1,6-diisocyanatohexane with a deficit of water or in the presence of water-releasing reactants in a known manner, essentially having biuret groups and having an average NCO content of 19-24% by weight.
• B) Among the polyalkylene oxide alcohols, amines and / or thiols of the formula 1, the polyalkylene oxide alcohols are preferred (Z = O in formula 1). From the polyalkylene oxide alcohols can be obtained by reaction with NH ₃ polyalkylene oxide amines (Z = NH in formula 1) and with H ₂ S polyalkylene oxide thiols (Z = S in formula 1).
  The polyalkylene oxide alcohols on which the polyalkylene oxide amines and thiols are also based therefore contain on average 3-70, preferably 6-60 and in particular 7-20 alkylene oxide units per molecule and can be obtained in a manner known per se by alkoxylation of suitable starter molecules. Compounds of the formula R ¹ R ² NH can be used as starter molecules. Depending on the meaning of R ¹ and R ^2, these are secondary amines or acid amides. According to the definition of R ¹ and R ^{2 given} for formula 1, morpholine can also be used as the heterocyclic nitrogen compound to start the alkoxylation reaction. Identical compounds are also obtained if compounds of the formula R ¹ R ² N-CHX-CHY-OH are used as starter molecules for the alkoxylation reaction, such as, for. B. 2-Morpholinoethanol. Also usable as starters are also acylation products of ethanolamine, e.g. B. acetyl ethanolamine.
  Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used individually or in succession in any order or together in a mixture for the alkoxylation. In this case, the polyalkylene oxide alcohols are based either on pure polyethylene oxides or mixed polyethylene oxides / propylene oxides. Particularly suitable are those polyalkylene oxide alcohols which contain on average 3-70, preferably 6-60 and in particular 7-20 alkylene oxide units per molecule and in which the alkylene oxide units are preferably at least 60 mol%, preferably at least 70 mol%, of Ethylene oxide units exist.
• C) The NCO-reactive compounds which contain anionic, cationic and / or potential anionic or cationic groups are usually
  • a) hydroxy- or amino-functional compounds with tertiary amino groups, as described in German patent application DE-OS-43 19 571, to which reference is hereby expressly made,
  • b) hydroxy- or amino-functional compounds with carboxyl or sulfonic acid groups, as are described in German patent application DE-OS-195 20 092, to which express reference is hereby made,
  • c) hydroxy- or amino-functional compounds with carboxylate or sulfonate groups, the counterions of which are metal cations from the alkali or alkaline earth group or ammonium ions, as are also described in DE-OS-195 20 092,
  • d) Hydroxy- or amino-functional compounds with ammonium groups which are obtainable in a manner known per se by alkylation or protonation, as described in EP-A-0 582 166, from the tertiary amino groups of the compounds i).
    Of course, any mixtures of such NCO-reactive compounds, if chemically useful, for example from groups i) and iv) or from groups ii) and iv) can be used in the process according to the invention.
• D) The auxiliary substances and additives which may be present are for example, wetting agents, surfactants, anti-foaming agents or misting agents tools. These auxiliaries and additives can either be inert or else be reactive towards the isocyanate groups.

The unmodified polyisocyanates I to be used according to the invention can also in combination with external, d. H. additional ionic or nonionic Emulsifiers are used. Such emulsifiers are for example in Methods of Organic Chemistry, Houben-Weyl, Vol. XIV / 1, Part 1, page 190-208 Thieme-Verlag, Stuttgart (1961) and in US-A-3,428,532 and EP-A-0 013 112 described. The emulsifiers are guaranteed in a dispersibility performing amount used.

If polyisocyanates I) are first reacted with polyalkylene oxide alcohols II), this reaction can be carried out in a manner known per se, while maintaining an NCO / OH equivalent ratio of at least 2: 1, generally from 4: 1 to about 1000: 1. When using polyethylene oxide alcohols, polyethylene oxide-modified polyisocyanates are obtained which have an average NCO functionality of 1.8-4.2, preferably 2.0-4.0, a content of aliphatic or cycloaliphatic isocyanate groups of 12.0- 21.5% by weight and a content of ethylene oxide units arranged within polyethylene oxide chains, calculated as C ₂ H ₄ O with a molecular weight of 44 g / mol, of 2-20% by weight, the polyethylene oxide chains on average Have 3-70 ethylene oxide units.

The starting components I), II) and optionally III) can be in any Order excluding moisture, preferably without solvent, be implemented. With increasing amount of component II), a higher Vis final product achieved. If the viscosity rises above 100 mPa.s, so it makes sense to work in the presence of a solvent, preferably with Water miscible but inert to the polyisocyanate. Appropriate solution means are z. B. alkyl ether acetates, glycol diesters, toluene, carboxylic acid esters, acetone, Methyl ethyl ketone, tetrahydrofuran and dimethylformamide.

By using catalysts known per se, such as dibutyltin dilaurate, tin (II) octoate or 1,4-diazabicyclo [2.2.2] octane, in amounts of 10-1000 ppm, based on components I), II) and, if appropriate III), the implementation of the components can be accelerated. The reaction is carried out in the temperature range up to 130 ° C., preferably in the range from 10-100 ° C. and particularly preferably from 20 to 80 ° C. The course of the reaction is followed by determining the NCO content by titration or by recording IR spectra and evaluating the NCO band at 2260-2275 cm ^-1 . The reaction is complete when the isocyanate content is not more than 0.1% by weight above the value which is achieved for a given stoichiometry in the case of complete conversion. As a rule, response times of less than 24 hours are sufficient. The solvent-free synthesis of the self-dispersing isocyanates to be used according to the invention is preferred.

In a further embodiment, it is also possible to prepare the self-dispersing isocyanates to be used according to the invention in step b) by mixing

• 1. unmodified polyisocyanates I),
• 2. Polyisocyanates obtained by reacting polyisocyanates I) with NCO reactive compounds III) are obtained, the equivalent ratio  the NCO-reactive groups of the compounds III) to the NCO- Groups of component I) 1: (1-1000), and
• 3. polyisocyanates obtained by reacting polyisocyanates I) with poly alkylene oxide alcohols, amines and / or thiols II) are obtained, wherein the equivalent ratio of the NCO-reactive groups of component II) the NCO groups of component I) used 1: (1-1000).

In this manufacturing variant, the number of NCO-reactive equivalents is the Polyalkylene oxide content, the NCO content and the NCO functionality through ent to adjust speaking weights of the above three components by a person skilled in the art, that the mixture obtained has the required for water dispersibility composition, whereby the preferred areas already mentioned apply.

The self-dispersible isocyanates are technically easy to handle and many Stable for months without moisture.

The self-dispersible isocyanates are in step b) of the invention Process preferably used without organic solvents. Because of your These isocyanates are self-dispersible at temperatures up to 100 ° C in water easy to emulsify without exposure to high shear forces. The isocyanate The concentration in the emulsion can be up to 70% by weight. But it is more advantageous, emulsions with an isocyanate concentration of up to 50% by weight produce, which may then be further diluted before the dosing point can be. Mixtures customary in industry are suitable for emulsification aggregates (stirrer, mixer with rotor-stator principle or high-pressure emulsifier machinery). A static mixer is usually sufficient. The received Emulsions have a processing time of up to 24 hours, which of the Structure of the self-dispersible isocyanates used, in particular of their Content of basic N atoms depends.  

Treatment of wool with an aqueous dispersion of self-dispersing Isocyanates in step b) are carried out by customary methods of the prior art. For example, a discontinuous procedure in the pull-out is suitable driving or a continuous way of working by diving, roller application, Padding, spraying, spraying or lisseuse application if necessary using dyeing machines, agitators etc. to move the loading action fleet. The fleet ratio can be selected within wide limits and can be in Range from 1: (5-20), preferably from 1: (5-10).

The following substance classes are in step c) of the method according to the invention usable as plasticizers: fatty acid amides, esterquats, quaternary fatty acid amides, Betaines, fatty acid sarcosides, aminosilicones, polyethylene wax emulsions, silicone emulsions.

In step d) of the method according to the invention, the wool material is ge possibly treated with anti-slip agents. Preferably, the fiction includes Proper procedures all three post-treatment steps b), c) and d). At the push-fit means are finishes which cause that in fabrics and knitted fabrics, which are later made from the wool, shifting the weft and warp threads against each other is prevented. In principle, a distinction is made with the sliding solid means those that cause roughening of the fiber surface and those that dull the fiber surface and the threads can stick together.

In particular, silica sols are suitable as sliding solid agents for roughening the fiber surface. These are aqueous solutions of approximately spherical, colloidally undissolved polysilicic acid molecules with an SiO ₂ content of usually 30-60%. Such silica sols can be stored unchanged for years. Depending on the particle size of the particles, silica sol is milky cloudy to colorless clear. The average particle diameter is usually 5-150 nm. The basic preparation is carried out by treating aqueous alkali silicate solutions (water glass) with ion exchangers and stabilizing them with little alkali. The silica sols are commercially available in various settings (anionic, cationic and nonionic).

In the case of the sliding solid agents, which blunt the fiber surface and the threads stick, it is mainly plastic dispersions and natural resins. Ge Plastic dispersions on a polyvinyl, polyacrylic, Polymethacrylic, polystyrene or polybutadiene base. Poly are particularly suitable vinyl alcohols, polyacrylates and blocked isocyanate resins and hydrophilized Isocyanate resins.

The application of the plasticizers in step c) and the anti-slip agents in step d) of the process according to the invention takes place either discontinuously in the pull-out process or continuously by dipping, roller application, padding, opening spraying, spraying or lisseuse application.

The isocyanate b) is 0.1-5% by weight, preferably 0.5-2.5% by weight, based on the total weight of the fleet used. The plasticizer c) is with 1-4 wt .-%, preferably used with 2-4 wt .-%, based on the total weight of the liquor. The anti-slip agent is used in an amount of 0.1-2% by weight, preferably 0.2-0.5 % By weight, based on the total weight of the fleet, used.

The order of the after-treatments b), c) and d) of the step a) above Traded wool material can also be varied so that the Nachbe acts b) and c) are carried out together and then the after treatment with the anti-slip agent according to d) is carried out. It is also possible Lich, first the after-treatment according to c), then according to b) and finally ge according to d).

If an anionic or cationic silica sol is used as the sliding solid agent d) the post-treatment steps are preferably in the order b), c), d) or c), b), d).

Claims (12)

1. Felt-free finished wool, characterized in that the wool

• a) is exposed to plasma in a pretreatment,
• b) optionally treated with an aqueous dispersion of self-dispersing isocyanates,
• c) then with a plasticizer as well
• d) is finally treated with an anti-slip agent.

2. Felt-free finished wool according to claim 1, characterized in that it the wool around raw wool after the raw wool wash, dyed or un dyed woolen roving, dyed or undyed wool yarn, knitted, knitted fabrics or fabrics. 3. Felt-free finished wool according to claim 1 or 2, characterized in that the self-dispersing isocyanates used in step b) have an iso cyanate content of 1-25% by weight, calculated as NCO (with a molecular weight of 42 g / mol) and are available through implementation in any order from

• A) with organic polyisocyanates with an average NCO functionality of 1.8-4.2
• B) polyalkylene oxide alcohols, amines and / or thiols of the formula 1,
  R ¹ R ² N- (CHX-CHY-O) _n -CHX-CHY-ZH (1)
  in which
  n represents a number from 3-70,
  X and Y are hydrogen or methyl, where in the event that one of the radicals X or Y is methyl, the other must be hydrogen,
  R ¹ and R ^{2 are} independently straight or branched C ₁ - C ₆ alkyl radicals or straight-chain or branched C ₁ -C ₆ acyl radicals, wherein for the case that R ¹ is a linear or branched C ₁ -C ₆ acyl radical is , R ^{2 can} also be hydrogen, and furthermore R ¹ and R ² together can also form a - (CH ₂ ) _m - alkylene radical with m = 4, 5, 6 or 7, in which one or two CH ₂ groups are represented by O and / or NH can be replaced and / or one or two CH ₂ groups can be substituted by methyl, and
  Z represents O, S or NH,
  and if necessary
• C) further NCO-reactive compounds which contain anionic, cationic and / or potentially anionic or cationic groups,
  and if necessary
• D) other auxiliaries and additives.

4. Felt-free finished wool according to claim 3, characterized in that the organic polyisocyanates I) unmodified, aliphatic, cyclo aliphatic, araliphatic or aromatic isocyanates with a medium NCO functionality from 1.8-4.2 are.   5. Felt-free finished wool according to claim 3, characterized in that the polyalkylene oxide alcohols, amines and / or thiols according to formula 1 in statistical mean 6-60 and preferably 7-20 alkylene oxide units per mole cool included. 6. Felt-free finished wool according to claim 5, characterized in that it are polyethylene oxide / propylene oxide alcohols, amines and / or thiols acts, preferably a proportion of at least 60 mol%, preferably at least 70 mol% of ethylene oxide units, based on the sum of Ethylene oxide and propylene oxide units have. 7. Felt-free finished wool according to claim 3, characterized in that the NCO-reactive compounds III)

• a) hydroxy- or amino-functional compounds with tertiary amino groups,
• b) hydroxy- or amino-functional compounds with carboxyl or sulfonic acid groups,
• c) hydroxy- or amino-functional compounds with carboxylate or sulfonate groups, the counterions of which are metal cations from the alkali or alkaline earth group or ammonium ions, or
• d) hydroxy- or amino-functional compounds with ammonium groups which can be obtained from the tertiary amino groups of the compounds i) by alkylation or protonation,

represent. 8. Felt-free finished wool according to one or more of claims 1-7, characterized in that fatty acid amides as plasticizers in step c), Ester quats, quaternary fatty acid amides, betaines, fatty acid sarcosides, amino  silicone, polyethylene wax emulsions or silicone emulsions are used become. 9. Felt-free finished wool according to one or more of claims 1-8, characterized in that in step d) anionic as a sliding solid or cationic silica sols, blocked isocyanate resins, hydrophilized iso cyanate resins, polyacrylates or polyvinyl alcohols can be used. 10. A method for felt-free finishing of wool, characterized in that the wool

• a) is exposed to plasma in a pretreatment,
• b) optionally treated with an aqueous dispersion of self-dispersing isocyanates,
• c) then with a plasticizer as well
• d) is finally treated with an anti-slip agent.

11. A method for felt-free finishing of wool according to claim 10, characterized ge indicates that the aftertreatment b) of the step a) above traded wool material either discontinuously in the pull-out process or continuously by dipping, roller application, padding, spraying, Spraying or lisseuse application takes place. 12. A method for felt-free finishing of wool according to claim 10 or 11, there characterized in that the post-treatments b) and c) are pre-combined be taken and then the post-treatment d) becomes.