NZ526178A - Dyed nonfelting keratin fibres and preparation thereof - Google Patents

Abstract

A process for dyeing and anti-felt finishing of keratin fibres, in which the keratin fibres are exposed to three treatment steps, (a) plasma treatment; (b) treatment with an aqueous dispersion of a cationic polyurethane; and (c) dyeing. The steps are effected in any order. The process can utilize a wide variety of types of keratin fibres, preferably wool, but including animal hairs other than wool and also human hair.

Description

New Zealand Paient Spedficaiion for Paient Number 526178 526 17 8 Patents Form 5 N.Z. No.

NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION DYED NONFELTING KERATIN FIBRES AND PREPARATION THEREOF We, BAYER AKTIENGESELLSCHAFT, a German company of 51368 Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - INTELLECTUAL PROPERtV: OFFICE OF N.Z. 2 8 MAY 2003 received - 1 - (Followed by 1A) T,e A 36 096-Foreien Countries Wim/klu/NT Dyed nonfelting keratin fibres and preparation thereof The invention relates to dyed nonfelting keratin fibres, especially wool, and to a process for dyeing and antifelt finishing of keratin fibres, especially wool.

Keratin fibres include wool, other animal hairs and also human hair. Especially woven, loop-drawingly knitted and loop-formingly knitted fabrics of wool are of economic importance.

The textile processing industry still has a particular interest in reducing the felting tendency of wool in any form, especially of raw wool or unprocessed wool. The felting of wool is customarily reduced by finishing with specific auxiliaries.

Isocyanates and especially self-dispersing isocyanates have long been used as auxiliaries for the antifelt finishing of textiles. However, self-dispersing isocyanates, which have come to be preferred for use, frequently still do not provide a completely satisfactory antifelt finish on the treated textiles when used alone.

DE-A-198 587 34 (equivalent to EP 1 151 161 Al) and DE-A-198 587 36 (equivalent to EP 1 010 799 A2) disclose the antifelt finishing of wool through combination of a plasma treatment with an aftertreatment using such self-dispersing isocyanates. To apply these self-dispersing isocyanates to wool, it is first necessary to prepare aqueous dispersions. Since such dispersions have only a very limited shelf life because of the isocyanate end group crosslinking reactions which ensue in water, they can disadvantageously only be prepared relatively shortly before use in wool treatment.

DE-A-2 035 172 (equivalent to US-A 3 657 002) describes a method for rendering wool resistant to shrinkage by treating the wool with a polyurethane latex liquor, drying the fabric and subsequently curing the fabric. To be able to prepare useful finishing latices, it is necessary to use organic solvents and also external emulsifiers in the prepolymerization. The IPONZ JUL 2003 Le A 36 096-Foreign Countries prepolymers initially obtained are subsequently end-polymerized by adding a chain-extending agent.

DE-C-26 57 513 discloses a wool antifelt finishing process which employs reaction 5 products of polyisocyanates with hydroxyl-functional compounds.

DD 5381 describes a process for preparing hydrophilic basic polyurethanes from diisocyanates, diprimary aliphatic glycols which contain one or more basic tertiary nitrogen atoms in an open chain and diprimary glycols without basic nitrogen. 10 Possible uses mentioned for such products are very generally self-supporting films, fibre materials, textile sizes and finishes, annualizing agents and paper-sizing agents.

DD 5379 describes a process for preparing hydrophilic basic polyurethane from diisocyanates and nitrogenous glycols which contain, in the chain between the 15 hydroxyl groups, one or more tertiary nitrogen atoms whose third valences are saturated by univalent alkyl groups which do not have more carbon atoms than the shortest carbon chain between hydroxyl group and tertiary nitrogen. Possible uses mentioned for such products are very generally self-supporting films, fibre materials, textile sizes and finishes, annualizing agents and paper-sizing agents.

DD 5367 describes very specific polyurethanes, which are prepared from diisocyanates and N,N'-di[oxyalkyl]piperazines.

German patent application 100 600 48 (equivalent to EP 1 211 346 Al), unpublished at 25 the priority date of the present invention, describes a process for the antifelt finishing of wool by subjecting the wool to a treatment with an aqueous dispersion of cationic polyurethanes after a plasma treatment. With regard to the manner in which this treatment with the dispersion of cationic polyurethanes is carried out, it is merely observed that in principle any possible known finishing apparatus can be used. 30 - '' IPONZ JUL 2003 Le A 36 096-Foreisn Countries It is an object of the present invention to provide a process whereby dyed nonfelting keratin fibres, especially wool, can be made available at acceptable outlay in terms of apparatus.

The present invention provides a process for dyeing and antifelt finishing of keratin fibres, characterized in that the keratin fibres are exposed to three treatment steps, (a) a treatment with a plasma, (b) a treatment with an aqueous dispersion of cationic polyurethanes, and (c) a dyeing, which treatment steps (a), (b) and (c) can be carried out in any order.

The process according to the invention can utilize a wide variety of types of keratin fibres, or example wool, animal hairs other than wool and also human hair.

The process according to the invention is advantageous in that the steps which are needed to treat and finish keratin fibres, preferably wool, can be flexibly combined with each other and carried out using simple apparatus.

Preference is given to an embodiment (A) of the process according to the invention where the keratin fibres, preferably wool, first are exposed to a treatment with a plasma as per step (a), subsequently treated with an aqueous dispersion of cationic polyurethanes as per step (b), and this treatment as per step (b) occurs in the dyeing apparatus and is carried out either before or after the dyeing of the keratin fibres, preferably wool, as per step (c).

Le A 36 096-Foreign Countries -4 In a particularly preferred embodiment (Al) of the process according to the invention, the keratin fibres, preferably wool, first are exposed to a treatment with a plasma as per step (a), 5 - subsequently treated with an aqueous dispersion of cationic polyurethanes as per step (b), immediately before finally a dyeing of the wool as per step (c) occurs.

In a similarly particularly preferred embodiment (A2) of the process according to the 10 invention, the keratin fibres, preferably wool, first are exposed to a treatment with a plasma as per step (a), subsequently subjected to a dyeing as per step (c), and immediately before finally as per step (b) the treatment with an aqueous 15 dispersion of cationic polyurethanes occurs in the dyeing apparatus.

A further embodiment (B) of the process according to the invention is characterized in that the keratin fibres, preferably wool, are first subjected to a dyeing as per step (c), subsequently exposed to a treatment with a plasma as per step (a), and finally treated with an aqueous dispersion of cationic polyurethanes as per step (b).

The steps (a) to (c) may be followed, irrespectively of the order in which they were 25 carried out, by further finishing steps (d) with further auxiliary and additive materials.

Preferred wool for use in the process according to the invention can come from different stages of the wool processing line, for example loose fibre, wool slubbing, 30 wool yarn, wool roving, woven fabric, loop-drawingly knitted fabric or loop-formingly knitted fabric, piece goods and also fully fashioned articles composed of Le A 36 096-Foreign Countries wool. But it is also possible to use blends of wool with synthetic fibres such as polyamide or polyacrylonitrile and/or with natural fibres such as cotton.

The water content of the wool is customarily 4% to 40% by weight, preferably 5% to 5 30% by weight, more preferably 6% to 25% by weight and especially 8% to 15% by weight.

The plasma treatment of the keratin fibres, preferably wool, as per step (a) of the process according to the invention can occur either in the form of a low temperature 10 plasma treatment at reduced pressure or in the form of a corona treatment at atmospheric pressure.

The low temperature plasma treatment is described at length in DE 196 16 776 CI (equivalent to WO 97/41293 Al), explicitly incorporated herein by reference. The ^ keratin fibres, preferably the wool, are subjected to a high frequency discharge having a frequency of 1kHz - 3 GHz and a power density of 0.001 - 3 W/cm3 at a pressure of 10 — 10 mbar for a period of 1 - 600 seconds in the presence or absence of non-polymerizing gases.

The treatment preferably occurs under a pressure of 0.1 -1 mbar and over a period of 20 2-5 minutes.

The actual low temperature plasma is generated by feeding in electromagnetic radiation in the frequency range of 1 kHz - 3 GHz. In a preferred variant, the low temperature plasma is generated by a microwave discharge of 1 - 3 GHz (the power 25 density at the outcoupling is especially 0.1 - 15 W/cm ). The electromagnetic radiation can be supplied continuously or pulsed. A pulsed high frequency discharge having a pulsing frequency of up 10 kHz is especially advantageous.

When non-polymerizing gases are additionally used as plasma process gases, they 30 are introduced into the plasma treatment space at a flow rate of up to 200 1/h. Useful IPONZ JUL 2003 Le A 36 096-Foreisn Countries non-polymerizing gases are in particular oxygen, nitrogen, noble gases, especially argon, air or mixtures thereof.

The design and apparatus configurations of low temperature plasma reactors are 5 known per se. Preference is given to using an electrodeless reactor having an outcoupling for microwaves. The keratin fibres to be treated, preferably the wool, are preferably placed underneath the outcoupling unit. The distance of the keratin fibres and preferably of the wool from the outcoupling unit is preferably 1 - 30 cm and especially 2-10 cm. After the keratin fibres to be treated, preferably the wool, have 10 been introduced into the reactor, the reactor is suitably evacuated with vacuum pumps in such a way that the pressure during the plasma treatment is in the range of 10~2 - 10 mbar and preferably 0.1-1 mbar. A continuous flow-through operation is preferably carried out by applying specific vacuum locks which make it possible for the material to enter and exit without leakage.

Alternatively to this embodiment of the low temperature plasma treatment under low pressure, the keratin fibres and preferably the wool can also be subjected to a corona treatment at a pressure in the range of 100 mbar - 1.5 bar and preferably at atmospheric pressure. The corona treatment is described at length in DE-A-20 198 587 36 (equivalent to EP 1 010 799 A2), explicitly incorporated by reference.

The corona treatment subjects the keratin fibres and preferably the wool to a high frequency discharge having a power density of customarily 0.01 - 5 Ws/cm2 for a period of 1 - 60 seconds and preferably 2-40 seconds and especially 3-30 seconds in 25 the presence or absence 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 in the frequency range between 1 kHz - 1 GHz and preferably 1-100 kHz to electrodes, one 30 or both poles being provided with an insulator material. The alternating voltage can IPONZ ,5 JUL 2003 Le A 36 096-Foreien Countries be supplied either continuously or with individual pulses or with pulse trains and pauses in between.

The design and apparatus configurations of a corona reactor are known per se and 5 described for example in DE-A-197 31 562 (equivalent to EP 893 535 Al). The corona treatment is preferably carried out via electric discharges in the atmospheric pressure region, for which the wool to be treated is initially introduced into a sealed, tight treatment housing, charged there with the working gas, i.e. the abovementioned non-polymerizing gas, and subsequently exposed to an electric barrier discharge in a gap between at least 10 two treatment electrodes. The distance of the keratin fibres and preferably of the wool material from the treatment electrodes is 0 - 15 mm, preferably 0.1-5 mm and especially 0.3 - 2 mm. The treatment electrodes are preferably constructed as rotatable rolls, either or both of which are coated with electrically refractory dielectric material.

Performing the corona treatment at a pressure in the range from 100 mbar to 1.5 bar and preferably at atmospheric pressure has the advantage over the low pressure plasma treatment at 10" - 10 mbar that the apparatus configuration needed is very much less costly and inconvenient than in the case of the low pressure treatment. 20 Vacuum pumps are not required, nor is it necessary to fit special vacuum locks.

The special effect of the plasma treatment in step (a) of the process according to the invention might be explained as follows. The liquid present in the fibre desorbs from the fibre surface as water vapour/gas during the process. High energy electrons, ions 25 and also highly excited neutral molecules or radicals are formed and act on the surface of the fibre, the water desorbed from the fibre ensuring that particularly reactive particles are formed in the immediate vicinity of the respective fibre surface and these particularly reactive particles act on the surface.

The cationic polyurethanes used for step (b) have a weight average molecular weight of at least 5000, preferably at least 8000, more preferably at least 9000. The upper IPONZ' f 5 JUL 2003 Le A 36 096-Foreign Countries limit of the molecular weight is customarily 50,000, preferably 45,000 and more preferably 40,000.

The cationic polyurethanes are obtainable by reaction of organic polyisocyanates of the general formula (I) Q[NCO]p (I) p is from 1.5 to 5 and Q is an organic radical one or more bis- and/or polyhydroxy compounds which contain at least one tertiary nitrogen atom and at least two hydroxyl groups, the cationic character of the polyurethanes being generated by subsequent protonation or alkylation of the tertiary nitrogen atoms present in component (ii).

Optionally, additionally (iii) one or more bis- and/or polyhydroxy compounds which contain no nitrogen atoms and have molecular weights of 62 to 5000 are used to prepare the cationic polyurethanes used according to the invention.

Useful organic polyisocyanates (i) of the general formula (I) Q[NCO]p (I) (i) where and (ii) where Q and p are each as defined above, include for example the three following types: Le A 36 096-Foreign Countries 1) aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates which contain no isocyanurate, uretdione, allophanate, biuret or oxadiazine structures, 2) aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates which contain isocyanurate and/or uretdione and/or allophanate and/or biuret and/or oxadiazine structures, 3) isocyanate prepolymers which are obtainable by reaction of aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates and polyesters and/or poly ethers.

The aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates 2) having isocyanurate and/or uretdione and/or allophanate and/or biuret and/or oxadiazine structures may be prepared according to well-known prior art processes, for example from corresponding aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates belonging to the abovementioned type 1).

Isocyanate prepolymers 3) include for example reaction products of aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates belonging to the abovementioned type 1) and polyesters and/or polyethers, which reaction products may contain as yet unconverted, free diisocyanates.

Useful aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates as type 1) or for preparing types 2) and 3) include for example: 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethyl-pentane, 2,2,4-trimethyl-l,6-diisocyanatohexane, 1,3- and 1,4-diisocyanatocyclo-hexane, l-isocyanato-l-methyl-4-isocyanatomethylcyclohexane and 4,4'-diiso-cyanatocyclohexylmethane, 2,4- and 2,6-diisocyanato-l-methylbenzene, 4,4'- and 4,2'-diisocyanatodiphenylmethane and also any mixtures thereof.

Ls A 36 096-Foreign Countries Preferred examples of modified isocyanates 2) are: trimerization products of 1,6-diisocyanatohexane and also its biuret-based derivatives, mixtures of the uretdione and the trimerization products of 1,6-diisocyanatohexane, the uretdione of 2,4- and/or 2,6-diisocyanato-1 -methylbenzene.

Preferred examples of the isocyanate prepolymers 3) are: reaction products of 2,4-and/or 2,6-diisocyanato-l -methylbenzene or of 1,6-diisocyanatohexane with polyhydric alcohols, as for example the reaction products of 2,4- and/or 2,6-diisocyanato- 1 -methylbenzene with trimethylolpropane. given to organic polyisocyanates (i) of the general formula (I) Q[NCO]p (I) is from 1.5 to 5 and especially 2, and is selected from a group consisting of an aliphatic hydrocarbyl radical having 2 to 18 and especially 6 to 10 carbon atoms, a cycloaliphatic hydrocarbyl radical having 4 to 15 and especially 5 to 10 carbon atoms, an aromatic hydrocarbyl radical having 6 to 15 and preferably 6 to 13 carbon atoms and an araliphatic hydrocarbyl radical having 8 to 15 and preferably 8 to 13 carbon atoms.

Preferred bis- and/or polyhydroxy compounds (ii) are those of the general formula (II) HO-CCHR1 )m-NR2-(CH2R1 )n-OH (II) where n and m are independently from 1 to 6, R1 is independently at each instance hydrogen or a straight-chain or branched Ci-C4-alkyl radical in that the meaning of R1 can alternate between hydrogen and straight-chain or branched Ci-C4-alkyl from carbon atom to carbon atom along the (CHR1^ and (CHR1)™ alkylene chains, Preference is where P Q Le A 36 096-Foreien Countries " 11 " R2 is straight-chain or branched Ci-C2o-alkyl, preferably Ci-Cig-alkyl, Ci-Cio-cycloalkyl, preferably C5-C6-cycloalkyl, C6-Ci2-aryl, preferably phenyl, or a -(CH2)q-OH radical in which q is from 1 to 6.

As bis- and/or polyhydroxy compounds (ii) of the general formula (II) there may be mentioned for example: N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-methyl-1,5-dipentanolamine, N-ethyl-l,5-dipentanolamine, triethanolamine, reaction products of fatty amines with two moles of ethylene oxide or propylene oxide and alkoxylation products of the abovementioned compounds, preferably of tris[2-(2-hydroxyethoxy)ethyl]amine.

As bis- and/or polyhydroxy compounds (iii) which contain no nitrogen atoms and have molecular weights of 62 to 5000 there may be mentioned for example: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 2,2-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neo-pentylglycol, 2,5-hexanediol, 1,6-hexanediol, 3-methyl-l,5-pentanediol, 2,5-dimethylhexane-2,5-diol, 1,12-octadecanediol, diethylene glycol, dipropylene glycol, Methylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol and also further higher polyethylene and polypropylene glycols, glycerol, trimethylol-propane, 2-hydroxymethyl-2-methyl- 1,3-propanediol, 1,2,6-hexanetriol and penta-erythritol.

It is further possible to use polyethers and polyesters having a weight average molecular weight of up to 5000, preferably up to 3000, and more preferably up to 2000 as component (iii). Polyethers are obtainable by using the compounds which were mentioned above as bis- and/or polyhydroxy compounds as initiator molecules which are reacted with ethylene oxide, propylene oxide and/or butylene oxide according to known prior art methods. Polyesters are likewise obtainable from the Le A 36 096-Foreien Countries abovementioned bis- and/or polyhydroxy compounds, namely by esterification with industrially available di- or tricarboxylic acids according to known methods of the prior art.

It is particularly useful to carry out step (b) using cationic polyurethanes, which are obtainable by reaction of (i) organic polyisocyanates of the general formula (I) Q[NCO]p (I) where p is from 1.5 to 5 and especially 2, and Q is selected from a group consisting of an aliphatic hydrocarbyl radical having 2 to 18 and especially 6 to 10 carbon atoms, a cycloaliphatic hydrocarbyl radical having 4 to 15 and especially 5 to 10 carbon atoms, an aromatic hydrocarbyl radical having 6 to 15 and preferably 6 to 13 carbon atoms and an araliphatic hydrocarbyl radical having 8 to 15 and preferably 8 to 13 carbon atoms, and (ii) bis- and/or polyhydroxy compounds (ii) of the general formula (II) HO-(CHR1)m-NR2-(CH2R,)n-OH (II) where n and m are independently from 1 to 6 and are in particular the same and are from 1 to 3, R1 is independently at each instance hydrogen or a straight-chain or branched Ci-C4-alkyl radical in that the meaning of R1 can alternate between hydrogen and straight-chain or branched C]-C4-alkyl from carbon atom to carbon atom along the (CHR])n and (CHR')m alkylene chains, R2 is straight-chain or branched Ci-C2o-alkyl, preferably Ci-Cig-alkyl, Cj-Cio-cycloalkyl, especially Cs-Cg-cycloalkyl, C6-Ci2-aryl, especially Le A 36 096-Foreien Countries phenyl, or a -(CH2)q-OH radical in which q is from 1 to 6 and especially from 1 to 3, the cationic character of the polyurethanes being generated by protonation or alkylation of the tertiary nitrogen atoms present in the component (ii).

Step b) of the process according to the invention most preferably employs such cationic polyurethanes as are obtained by reaction of (i) 2,4-toluylene diisocyanate or 2,6-toluylene diisocyanate or 4,4'-diisocyanatodiphenylmethane or 2,4'-diisocyanatodiphenylmethane or mixtures of these isomers with (ii) N-methyl- or n-butyldiethanolamine the cationic character of the polyurethanes being generated by protonation of the tertiary nitrogen atoms present in the component (ii) by treatment of these reaction products with an acid selected from the group consisting of hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid and propionic acid.

The cationic polyurethanes to be used in step (b) of the process according to the invention are prepared by initially charging the bis- and/or polyhydroxy compounds (ii) and optionally (iii), customarily in an aprotic auxiliary solvent.

The amount of polyhydroxy compounds (ii) and optionally (iii) is preferably chosen such that the cationic polymer obtained is still readily processible.

Examples of useful aprotic solvents for the reaction are: alkyl ether acetates, glycol diesters, toluene, carboxylic esters, acetone, methyl ethyl ketone, tetrahydrofuran and dimethylformamide, N-methylpyrrolidone and propylene carbonate.

Le A 36 096-Foreign Countries Particular preference is given to methoxypropyl acetate, propylene glycol diacetate, butyldiglycol acetate and propylene carbonate.

This initially charged solution is then admixed with the organic polyisocyanate (i) by 5 stirring. It is important here to avoid excesses of organic polyisocyanate (i), since this leads to unwanted secondary reactions owing to the presence of a multiplicity of tertiary amine structures from the components (ii).

Conventional catalysts such as dibutyltin dilaurate, tin(II) octoate or 1,4-diaza-bicyclo[2,2,2]octane in amounts of 10 to lOOO ppm, based on the reaction components, can be used to speed up the reaction. The reaction is carried out in the temperature range up to 130°C, and preferably in the range between 20 and 80°C. The reaction temperature is limited at the upper end by the boiling point of the solvent; it can be advantageous to conduct the reaction under evaporative cooling. The reaction is monitored by measurement of the IR spectra and evaluation of the NCO band at 2260-2275 cm"1 and has ended when the NCO band has disappeared.

The molar ratio of component (i) to component (ii) plus optionally component (iii) is preferably chosen such that the NCO and OH end groups are present in an approximately stoichiometric ratio. (The stoichiometry of the reaction is 1:1 or close to the 1:1 value.) The polyurethanes can be rendered cationic in two ways: either by protonation or by alkylation of the tertiary nitrogen atoms present in component (ii).

In protonation, the reaction solution obtained after the reaction of the components (i), (ii) and optionally (iii) is diluted with an aqueous phosphoric acid. Examples of useful acids are hydrochloric acid, sulphuric acid, formic acid, acetic acid or propionic acid. Preference is given to formic acid and acetic acid. This addition of an 30 acid protonates the tertiary nitrogen atoms from component (ii). It is customary here to employ a stoichiometric amount of acid, based on the nitrogen atoms, to achieve Le A 36 096-Foreign Countries substantially complete protonation. The solvent is subsequently distilled off until the theoretical solids content is reached. In a less preferred embodiment, either all or else some of the solvent remains in the product.

\ In alkylation, the reaction solution obtained after the reaction of the components (i), (ii) and optionally (iii) is admixed with an alkylating agent. The alkylating agent used can be methyl chloride, methyl iodide, dimethyl sulphate or methyl p-toluene-sulphonate. The tertiary nitrogen atoms present in the components (ii) are partly or fully alkylated. This partial or full alkylation provides a polyurethane having permanent cationic charges.

Step (b) of the process according to the invention involves the cationic polyurethane (which is present in aqueous dispersion) being applied to the wool at a pH of 2 to 7, preferably 3 to 6, more preferably 4 to 6 and especially 4.5 to 5.5. The temperature at which this treatment with the aqueous dispersion of the cationic polyurethanes is carried out is customarily in the range from 20 to 80 °C, preferably 30 to 70 °C and more preferably 30 to 60 °C.

The concentration of aqueous cationic polyurethane in the finishing liquor is in the range from 0.1 to 75 g/1 of finishing liquor and preferably in the range from 0.5 to 50 g/1 of finishing liquor, based on polyurethane solids.

The liquor ratio is choosable within wide limits and can range from 5 : 1: to 40 : 1 and is preferably in the range from 5 : 1 to 30 : 1.

Unexpectedly, the cationic polyurethanes automatically go onto the keratin fibres, preferably the wool, in step (b) of the process according to the invention. This is all the more astonishing as wool, at the customarily employed, slightly acidic pH of the aqueous liquor, will itself have a cationically charged surface, which should actually repel the cationic polyurethanes and which should consequently result in worse affinity of the polyurethanes for wool.

Le A 36 096-Foreign Countries' The dyeing of the keratin fibres, preferably wool, as per step (c) of the process according to the invention can occur with various dye classes (half-milling/milling, milling, 1:2 metal complex dyes with and without sulpho groups, afterchroming and reactive dyes). Surprisingly, all the aforementioned dyes, contrary to all experiences with wool which has been the dyeing of keratin fibres, preferably Hercosett-treated wool, succeed in achieving superwash fastnesses as required by the Woolmark Company Test Methods TM 174 (perspirationfastness, alkaline) and TM 193 (domestic machine washing at 50°C).

Embodiment (A) of the process according to the invention is carried out by first performing the plasma treatment of the keratin fibres, preferably wool, as per step (a). The treatment of the keratin fibres, preferably wool, as per step (b) with the aqueous dispersion of cationic polyurethanes can occur either before (embodiment (A 1)) or after (embodiment (A2)) of the dyeing as per step (c), in the same dyeing apparatus in which the dyeing is carried out.

The two treatment steps (a) and (b) (embodiment (Al)) or (a) and (c) (embodiment (A2)), however, need not necessarily be carried out directly in succession. On the contrary, an intervening textile processing operation can occur, for example in the form of spinning, weaving, drawn-loop knitting, formed-loop knitting or making-up.

It is thereby possible, for example, first to produce piece goods after step (a) and only afterwards to dye them as per step (c) and then to give them a nonfelting finish as per step (b). As well as providing increased commercial flexibility, this permits, especially with regard to dyeing, a faster response to any short-term changes in modish colours.

In the case of embodiments (Al) and (A2), the treatment as per step (b) occurs in the dyeing apparatus preferably immediately before or immediately after the dyeing of the keratin fibres, preferably wool, as per step (c). "Immediately" in this context Le A 36 096-Foreien Countries means that no other finishing steps occur between the treatments as per step (b) and subsequently step (c) (embodiment (Al)) or as per step (c) and subsequently step (b) (embodiment (A2)). What is allowed in between at most, if desired, is the performance of one or more rinsing operations and also the setting of a desired pH.

Useful dyeing apparatus for conducting step (b) in the case of embodiment A includes any prior art dyeing apparatus suitable for dyeing keratin fibres, preferably wool in the form of loose fibre, slubbing, roving, yarn, whether as package or hank, woven fabric, loop-formingly knitted fabric and loop-drawingly knitted fabric and also piece goods as well as fully fashioned articles composed of wool or else blends of wool with synthetic fibres, for example polyamide or polyacrylonitrile, and/or with natural fibres such as cotton and also regenerated cellulose fibres such as viscose or lyocell.

The main advantage of the embodiments (Al) and (A2) is that the keratin fibres, preferably wool, which have to be dyed as well as be given a nonfelting finish, can selectively either be first dyed and then finished or first finished and then dyed, and that the two operations can be carried out immediately successively in the same apparatus.

This not only provides increased commercial flexibility with regard to dyeing and finishing but also a not inconsiderable labour saving. For instance, it eliminates the need for operations such as the emptying of the dyeing apparatus after dyeing and a subsequent separate finishing of the dyed material, for example on a backwasher. A further advantage is the energy saving, since the wool has to be dried only once, depending on the manner of further processing.

In the case of embodiment (B) of the process according to the invention, it is possible for the keratin fibres, preferably wool, to be initially dyed as per step (c) and for the dyed keratin fibres, preferably wool, only subsequently to be subjected to the treatment with the plasma as per step (a) and to the treatment with the dispersion of Le A 36 096-Foreign Countries ■ • • • cationic po hair ethanes as per step (b). The treatment of the keratin fibres, preferably wool, as per step (b) can occur according to well-known finishing processes of the prior art and in any suitable apparatus. An example of a suitable process is a batch operation in an exhaust process or a continuous operation by dipping, kiss roll 5 application, pad-mangling, spraying, slop-padding, pouring on or backwasher application.

The process in which the keratin fibres, preferably wool, are treated according to the invention, with the steps (a),(b) and (c) being carried out in any desired order, 10 preferably in the order (a),(b),(c) (embodiment Al), (a),(c),(b) (embodiment A2) or (c),(a),(b) (embodiment B), may optionally be followed by a further aftertreatment step (d) in which the keratin fibres, preferably wool, are treated with further auxiliaries and additive materials. Useful such auxiliaries and additive materials include for example levelling agents, surfactants, deaerators, wetting agents, 15 dispersing agents, fixing agents, plasticizers and also antistats. This further aftertreatment step is advantageously likewise carried out in the same apparatus as whichever is the preceding step, i.e. in a dyeing apparatus in the case of embodiments Al and A2 and in the particular apparatus used for the treatment as per step (b) in the case of embodiment B.

The cationic polyurethanes used in the process according to the invention are incomparably more stable in aqueous dispersion than the self-dispersing isocyanates known from DE-A-198 587 34 (equivalent to EP 1 151 161 Al) and DE-A-198 587 36 (equivalent to EP 1 010 799 A2). The corresponding dispersions therefore do not have to be used by a set date and can be produced long 25 ahead of when they are used. In addition, the cationic polyurethanes applied in the process according to the invention are very stable to laundering. This holds in particular when the dispersion of the cationic polyurethanes is prepared using, as component (ii), substances of the formula (II) that are reaction products of fatty amines with two moles of ethylene oxide or propylene oxide.

IPONZ JUL 2003 Le A 36 096-Foreign Countries ... „ The keratin fibres, preferably wool, which have been dyed and finished with cationic polyurethanes differ distinctly from wool finished with self-dispersing isocyanates. The self-dispersing isocyanates known from DE-A-198 587 34 (equivalent to EP 1 151 161 Al) and DE-A-198 587 36 (equivalent to EP 1 010 799 A2) are low molecular weight compounds which are prepared for example by 5 reacting organic diisocyanates such as diisocyanatobutane with monofimctional polyalkylene oxide alcohols, polyalkylene oxide amines or polyalkylene oxide thiols. These self-dispersing isocyanates undergo crosslinking on the surface of wool in the presence of water. The NCO end groups of the polyisocyanates react with the water to detach CO2 and form networks by forming urea linkages between two isocyanate 10 molecules at a time. The crosslinked, longer chains thus possess a relatively large number of urea moieties and only very few urethane bonds. In contrast, the polyurethanes, having the indicated higher molecular weights in the backbone, possess a very large number of urethane bonds. Owing to the higher molecular weights, the end group concentration is relatively low and the end groups themselves 15 are difficult to access. It is accordingly unlikely that any small amount of NCO end groups present will undergo crosslinking through the influence of water.

IPONZ JUL 2003 Le A 36 096-Foreign Countries Examples: I Preparation of cationic polyurethanes Polyurethane 1: (inventive) 174.5 g of toluylene diisocyanate (80 : 20 mixture of 2,4- and 2,6-isomers; 1.003 mol in total) are added to a solution of 119.2 g of N-methyldiethanolamine in 250 g of acetone at room temperature in the course of 1.5 hours. An infrared spectrum is then recorded to check for the presence of free isocyanate groups. When free isocyanate groups are no longer present, 707 g of water and 60 g of glacial acetic acid are added as a mixture. A homogeneous clear liquid is formed. The solvent is distilled off until a solids content of 29% is reached.

Polyurethane 2: (inventive) 168.8 g of toluylene diisocyanate (80 : 20 mixture of 2,4- and 2,6-isomers; 1.003 mol in total) are added to a solution of 119.2 g of N-methyldiethanolamine in 250 g of acetone at room temperature in the course of 1.5 hours. An infrared spectrum is then recorded to check for the presence of free isocyanate groups. When free isocyanate groups are no longer present, 696 g of water and 60 g of glacial acetic acid are added as a mixture. A homogeneous clear liquid is formed. The solvent is distilled off until a solids content of 29% is reached.

II Finishing of wool and nonfelting test Plasma pretreatment The plasma treatment of the wool in the finishing examples which follow is always carried out as follows: Le A 36 096-Foreign Countries 21 - First, moist wool slubbing is subjected to a corona treatment using the following parameters: roll distance: 0.8 mm air feed: 400.0 m3/h pulse on: 4 full cycles pulse off: 7 full cycles spreading: 1:2 forward feed rate: 5 m/min power: 4X 3.0 kW Example 1: (Order of treatment steps: (a),(b),(c) (embodiment Al); dyeing (c) with metal complex dyes having a sulpho group) Step (b): 500 kg of the wool slubbing plasma-treated as per step (a) are rinsed with acetic acid at 40°C for 20 minutes to adjust the pH to 4.5-5 in a slubbing dyeing apparatus (atmospheric or sealed). The wool is then treated for 20 minutes at 40 °C with 5 m3 of a finishing liquor having the following components: 12 g/1 of polyurethane 2 1.5 g/1 of acetic acid 60% 3.0 g/1 of sodium acetate, anhydrous.

After this treatment, the liquor is dropped.

Le A 36 096-Foreign Countries Step (c): The wool is then treated for 60 minutes at 98 °C with 5000 1 of a dyeing liquor having the following components: 0.3% of Isolan® GelbS-GL 0.3% of Isolan® Rot S- RL 0.5% of Isolan® Grau S-GL 1.0 g/1 of sodium sulphate calcined 3.0% of acetic acid 60% (sufficient for a pH of 4.5) 1.0% of Avolan® S J After the dyeing operation, the dyeing liquor is dropped and the dyed material is rinsed at 40 °C with water for 20 minutes and then dried.

The colour fastnesses of the wool thus dyed and given a nonfelting finish are tested to the Woolmark Company Test Methods TM 174 (perspirationfastness, alkaline) and TM 193 (domestic machine washing at 50°C) and are found to meet the requirements.

Example 2: (Order of treatment steps: (a),(c),(b) (embodiment A2); dyeing (c) with metal complex dyes without sulpho group) Step (c): 500 kg of the wool slubbing plasma-treated as per step (a) are rinsed with acetic acid at 40°C for 20 minutes to adjust the pH to 4.5-5 in a slubbing dyeing apparatus (atmospheric or sealed). The wool is then treated for 60 minutes at 98 °C with 5000 1 of a dyeing liquor having the following components: Le A 36 096-Foreign Countries 0.6% of Isolan® Gelb K-PRL 200% 0.6% of Isolan® Bordeaux R 220% 0.55% of Isolan® Grau K-PRL 200% 1.0 g/1 of sodium sulphate calcined 3.0% of acetic acid 60% (sufficient for a pH of 4.5) 1.0% of Avolan® S After the dyeing operation, the dyeing liquor is dropped and the dyed material is rinsed at 40 °C with water for 20 minutes.

Step (b): The wool is then treated for 20 minutes at 40 °C with 5 m3 of a finishing liquor having the following components: 12 g/1 of polyurethane 2 1.5 g/1 of acetic acid 60% 3.0 g/1 of sodium acetate, anhydrous.

After this treatment, the liquor is dropped, the wool is rinsed with water and subsequently dried.

The colour fastnesses of the wool thus dyed and given a nonfelting finish are tested to the Woolmark Company Test Methods TM 174 (perspirationfastness, alkaline) and TM 193 (domestic machine washing at 50°C) and are found to meet the requirements.

Le A 36 096-Foreign Countries Example 3: (Order of treatment steps (a),(c),(b) (embodiment A2); dyeing (c) with reactive dyes) Step (c): kg of a wool slubbing plasma-treated as per step (a) are treated in a slubbing dyeing apparatus (atmospheric or sealed) for 90 minutes at 98 °C with 300 1 of a dyeing liquor having the following components: 0.165% of Remazol® Brillantgelb GL 150% 0.11 % of Realan® Rot 2.8% of Realan® Marineblau R 1.0% of Avolan® RW 3.0% of acetic acid 60% (sufficient for a pH of 4.5) After this treatment, the liquor is dropped; an aftertreatment is carried out with an aqueous 0.0015% ammonia solution at a pH of 8.5 at 80°C for 20 minutes.

This is followed by two rinses with water and then the wool is then rendered slightly acidic using dilute acetic acid..

Step (b): The wool is then treated for 20 minutes at 40 °C with 3001 of a finishing liquor having the following components: 12 g/1 of polyurethane 2 1.5 g/1 of acetic acid 60% 3.0 g/1 of sodium acetate, anhydrous.

The wool is dried without rinsing.

Le A 36 096-Forei,gn Countries The colour fastnesses of the wool thus dyed and given a nonfelting finish are tested to the Woolmark Company Test Methods TM 174 (perspirationfastness, alkaline) and TM 193 (domestic machine washing at 50°C) and are found to meet the requirements.

Example 4: (Order of treatment steps: (a),(c),(b) (embodiment A2); dyeing with acid dyes) Step (c): kg of a wool slubbing plasma-treated as per step (a) are treated in a slubbing dyeing apparatus (atmospheric or sealed) for 90 minutes at 98 °C with 3001 of a dyeing liquor having the following components: 0.51% of Supranol® Goldgelb S-WP 01 1.36% of Supranol® Rubin S-WP 0.58% of Supranol® Blau S-WP 01 1.0 g/1 of sodium sulphate calcined 3.0% of acetic acid 60% (sufficient for a pH of 4.5) 100% of Avolan® S.

After the drying, the liquor is dropped and the dyed material is rinsed at 40° C on the dyeing machine.

Le A 36 096-Foreign Countries Step (b): The wool is then treated for 20 minutes at 40 °C with 3001 of a finishing liquor having the following components: 12 g/1 of polyurethane 2 1.5 g/1 of acetic acid 60% 3.0 g/1 of sodium acetate, anhydrous.

The wool is dried without rinsing.

The colour fastnesses of the wool thus dyed and given a nonfelting finish are tested to the Woolmark Company Test Methods TM 174 (perspirationfastness, alkaline) and TM 193 (domestic machine washing at 50°C) and are found to meet the requirements.

Example 5: (Order of treatment steps: (a),(c),(b) (embodiment A2)) Step (c): kg of a wool slubbing plasma-treated as per step (a) are treated in a slubbing dyeing apparatus (atmospheric or sealed) for 45 minutes at 98 °C with 300 1 of a dyeing liquor having the following components: 4.5% of Diamant® Schwarz PV 200% 3.0% of acetic acid 60% (having a pH of 4.5) 0.5% of Avolan® S.

After a dyeing time of 45 min, the dyebath has added to it 1.0% of 85% formic acid with the steam switched off. The dyebath is again brought to the boil. At the boil, dyeing is continued for a further 20 min.

Le A 36 096-Foreien Countries The fresh bath which then follows is adjusted to pH 3.5 to 3.8 with 85% formic acid. This is followed by the addition of 1.58% of K2Cr207. The chroming bath is gradually brought to the boil. At the boil, chroming is carried out for 30 min. After 5 the chroming operation, the liquor is dropped, the wool is rinsed twice with water in the dyeing apparatus and the pH of the wool is adjusted to 4.5-4.8 by rinsing with an aqueous 0.0015% ammonia solution.

Step (b): The wool is then treated for 20 minutes at 40 °C with 300 1 of a finishing liquor having the following components: 12 g/1 of polyurethane 2 15 1.5 g/1 of acetic acid 60% 3.0 g/1 of sodium acetate, anhydrous.

The wool is dried without rinsing.

The colour fastnesses of the wool thus dyed and given a nonfelting finish are tested to the Woolmark Company Test Methods TM 174 (perspirationfastness, alkaline) and TM 193 (domestic machine washing at 50°C) and are found to meet the requirements.

III Antifelting tests of dyed nonfelting wool: After drying, the wool of examples 1-4 is subjected to the Aachen felting ball test of IWTO standard 20-69. The results are summarized in table 1 below. The values reported are averages of a double determination.

Claims (19)

Le A 36 096-Foreign Countries -28- Example Felt density Felting ball diameter [g/cm3] [cm] 2 0.044 3.506 3 0.048 3.415 4 0.049 3.398 5 0.045 3.477 The values observed for the quality of the antifelting finish must be considered very good - irrespectively of the order of the treatment steps (a), (b) and (c). Le A 36 096-Foreien Countries -29- Patent Claims

1. Process for dyeing and antifelt finishing of keratin fibres, characterized in that the keratin fibres are exposed to three treatment steps, (a) a treatment with a plasma, (b) a treatment with an aqueous dispersion of cationic polyurethanes, and (c) a dyeing, which treatment steps (a), (b) and (c) can be carried out in any order.

2. Process according to Claim 1, characterized in that the keratin fibres used are wool.

3. Process according to Claim 1, characterized in that the keratin fibres used are animal hairs other than wool or human hair.

4. Process according to Claim 1, characterized in that the keratin fibres, preferably wool, first are exposed to a treatment with a plasma as per step (a), subsequently treated with an aqueous dispersion of cationic polyurethanes as per step (b), and this treatment as per step (b) occurs in the dyeing apparatus and is carried out either before or after the dyeing of the keratin fibres, preferably wool, as per step (c).

5. Process according to Claim 4, characterized in that the keratin fibres, preferably wool, Le A 36 096-Foreien Countries -30- first are exposed to a treatment with a plasma as per step (a), subsequently treated with an aqueous dispersion of cationic polyurethanes as per step (b), immediately before finally a dyeing of the wool as per step (c) occurs. 5

6. Process according to Claim 4, characterized in that the keratin fibres, preferably wool, first are exposed to a treatment with a plasma as per step (a), 10 - subsequently subjected to a dyeing as per step (c), and immediately before finally as per step (b) the treatment with an aqueous dispersion of cationic polyurethanes occurs in the dyeing apparatus. 15

7. Process according to Claim 1, characterized in that the keratin fibres, preferably wool, are first subjected to a dyeing as per step (c), subsequently exposed to a treatment with a plasma as per step (a), 20 - and finally treated with an aqueous dispersion of cationic polyurethanes as per step (b).

8. Process according to one or more of Claims 1-7, characterized in that the plasma treatment of the keratin fibres, preferably of wool, as per step (a) 25 occurs either in the form of a low temperature plasma treatment at reduced pressure or in the form of a corona treatment at atmospheric pressure. 30

9. Process according to one or more of Claims 1-8, characterized in that the cationic polyurethanes to be used as per step (b) have a weight-average molecular weight of at least 5000, preferably at least 8000 and more Le A 36 096-Foreien Countries - 31 - preferably at least 9000 and the upper limit of the molecular weight is 50,000, preferably 45,000 and more preferably 40,000.

10. Process according to one or more of Claims 1-9, characterized in that the 5 cationic polyurethanes are obtainable by reaction of (i) organic polyisocyanates of the general formula (I) Q[NCO]P; (I) where 10 p is from 1.5 to 5 and Q is an organic radical and (ii) one or more bis- and/or polyhydroxy compounds which contain at least one tertiary nitrogen atom and at least two hydroxyl groups, 15 the cationic character of the polyurethanes being generated by subsequent protonation or alkylation of the tertiary nitrogen atoms present in component (ii). 20

11. Process according to Claim 10, characterized in that additionally (iii) one or more bis- and/or polyhydroxy compounds which contain no nitrogen atoms and have molecular weights of 62 to 5000 are used in the reaction to prepare the cationic polyurethanes. 25

12. Process according to Claim 10 or 11, characterized in that the bis- and/or polyhydroxy compounds (ii) have the general formula (II) HO-(CHR,)m-NR2-(CH2R1)n-OH (II) where n and m are independently from 1 to 6, 30 R1 is independently at each instance hydrogen or a straight-chain or branched Ci-C4-alkyl radical in that the meaning of R1 can alternate Le A 36 096-Foreign Countries -32- between hydrogen and straight-chain or branched Ci-Gralkyl from carbon atom to carbon atom along the (CHR1),, and (CHR1)™ alkylene chains, R is straight-chain or branched Ci-C2o-alkyl, preferably Ci-Cis-alkyl, Ci-Cio-cycloalkyl, preferably C5-C6-cycloalkyl, C6-Ci2-aryl, preferably phenyl, or a -(CH2)q-OH radical in which q is from 1 to 6.

13. Process according to Claim 12, characterized in that the bis- and/or polyhydroxy compounds (ii) of the general formula (II) are selected from the group consisting of N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-methyl-1,5-dipentanolamine, N-ethyl-1,5-dipentanol-amine, triethanolamine, reaction products of fatty amines with two moles of ethylene oxide or propylene oxide and alkoxylation products of the above-mentioned compounds, preferably of tris[2-(2-hydroxyethoxy)ethyl]amine.

14. Process according to one or more of Claims 10-13, characterized in that the bis- and/or polyhydroxy compounds (iii) are selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, 2,5-hexanediol, 1,6-hexanediol, 3-methyl-l,5-pentanediol, 2,5-dimethylhexane-2,5-diol, 1,12-octadecanediol, diethylene glycol, dipropylene glycol, Methylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol and also further higher polyethylene and polypropylene glycols, glycerol, trimethylolpropane, 2-hydroxymethyl-2-methyl-1,3-propanediol, 1,2,6-hexanetriol and pentaerythritol.

15. Process according to one or more of Claims 10-14, characterized in that the cationic polyurethanes are obtainable by reaction of (i) organic polyisocyanates of the general formula (I) Q[NCO]p (I) Le~A 36 096-Foreign Countries -33 - where p is from 1.5 to 5 and especially 2, and Q is selected from a group consisting of an aliphatic hydrocarbyl radical having 2 to 18 and especially 6 to 10 carbon atoms, a cycloaliphatic hydrocarbyl radical having 4 to 15 and especially 5 to 10 carbon atoms, an aromatic hydrocarbyl radical having 6 to 15 and preferably 6 to 13 carbon atoms and an araliphatic hydrocarbyl radical having 8 to 15 and preferably 8 to 13 carbon atoms, and (ii) bis- and/or polyhydroxy compounds (ii) of the general formula (II) HO-(CHR')m-NR2-(CH2R1)n-OH (II) where n and m are independently from 1 to 6 and are in particular the same and are from 1 to 3, R1 is independently at each instance hydrogen or a straight-chain or branched Ci-C4-alkyl radical in that the meaning of R1 can alternate between hydrogen and straight-chain or branched Ci-C4-alkyl from carbon atom to carbon atom along the (CHR!)n and (CHR1)™ alkylene chains, R2 is straight-chain or branched Ci-C2o-alkyl, preferably Q-Cig-alkyl, Ci-Cio-cycloalkyl, especially Cs-Cc-cycloalkyl, C6-C12-aryl, especially phenyl, or a -(CH2)q-OH radical in which q is from 1 to 6 and especially from 1 to 3, the cationic character of the polyurethanes being generated by protonation or alkylation of the tertiary nitrogen atoms present in the component (ii).

16. Process according to one or more of Claims 10-15, characterized in that the cationic polyurethanes used are obtainable by reaction of Le A 36 096-Foreign Countries -34- (i) 2,4-toluylene diisocyanate or 2,6-toluylene diisocyanate or 4,4'-diisocyanatodiphenyimethane or 2,4'-diisocyanatodiphenylmethane or mixtures of these isomers with (ii) N-methyl- or n-butyldiethanolamine, the cationic character of the polyurethanes being generated by protonation in the form of a treatment of these reaction products with an acid selected from the group consisting of hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid and propionic acid.

17. Process according to one or more of Claims 1-16, characterized in that step (b) is carried out by applying the aqueous dispersion of the cationic polyurethane to the wool at a pH of 2 to 7, preferably 3 to 6, more preferably 4 to 6 and especially 4.5 to 5.5.

18. Process according to one or more of Claims 1-17, characterized in that the concentration of the aqueous dispersion of the cationic polyurethane in the finishing liquor is 0.1 to 75 g/1 and preferably 0.5 to 50 g/1, based on polyurethane solids.

19. Dyed nonfelting keratin fibres, preferably wool, and textile processing products thereof, characterized in that the wool is obtainable by one or more of the processes according to Claims 1-18. 35 A process according to claim 1 substantially as herein described or exemplified. A dyed nonfelting keratin fibre and textile processing products thereof according to claim 19 substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT 3LL3C7UAL PROPERTY Or";CE OF N.z.