GB2102454A - Process for producing multicoloured anionic dyeings - Google Patents

Abstract

A wet-on-wet dyeing process for dyeing anionic dyeable substrates comprises A) applying locally to the substrate at room temperature, a liquor or paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH8-value>/=5, B) impregnating the substrate with an acid dyeing liquor containing an anionic dye having a K'pH6-value>/=5 C) subsequently submitting the substrate to a heat treatment to effect fixation of the dye. The alkylated fatty amines used fall within the formula: <IMAGE> in which R is (C10-24) alkyl or (C10-24) alkenyl X1 is -CO- or a direct bond, in each (A-O)x, (A-O)y and (A-O)z chain A is, independently, -CH2CH2- or -CH(CH3)-CH2-, each n is 2 or 3 independently, m is 0 or 1-6 and each x, y or z is 1-100, the sum x+y+z being 10-100 and is in the form of a free base, acid addition salt, quaternary ammonium salt or mixture thereof or mixtures of such compounds differing by virtue of the significance of R.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to a process for dyeing a substrate dyeable with anionic dyes to produce reserve or multicoloured effects with soft outlines.

The invention provides a process for dyeing an anionic dyeable substrate which process comprises A) applying locally to the substrate at room temperature a liquor or paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6-value > 5, followed by B) impregnating the substrate with an acid dyeing liquor containing an anionic dye having a K'pH6valuek5, and C) subsequently submitting the substrate to a heat treatment to effect fixation of the dye.

The liquors or paste of both steps (A) and (B) are applied at least to one common area of the substrate.

According to a further aspect of the invention, the liquor or paste of step (A) may contain, in addition to the alkoxylated fatty amine or polyamine, a disperse or anionic dye or a mixture thereof or an anionic optical brightening agent, provided that the anionic dye or anionic optical brightening agent has a K'pH6-valueA5 which is at least one unit lower than the K'pH6-value of the anionic dye used in step (B). As it will be appreciated, the dyes or optical brightening agent applied in step (A) are also fixed by the heat treatment of step (C).

The K'pH6-value represents the combinability value of an anionic dye experimentally assessed at pH6 in the presence of a cationic compound; this value is usually employed to indicate the combination capacity of anionic dyes [See GB Patent 1,489,456; Otten H.G., Bayer Farbenrevue, 21,32 (1972); and Beckmann W., Hoffman F. and Otten H. G., Melliand Textilber. 6,641 (1973)].The K'-value is a specific dyestuff characteristic which provides a practical indication of the behaviour in dyeing of an anionic dye in relation with its combination capacity. This value usually may vary from 1 to 10.

The K'pH6-value of the anionic dyes may be assessed according to the following test method with reference to a standard anionic dye whose K'pH6-value is known: Nylon yarn (Du Pont, type 846) is introduced at a goods to liquor ratio of 1:40 in a dyebath at 400 and pH6. This dyebath contains demineralized water, a standard anionic dye and the dye to be tested in an amount corresponding for each dye respectively to the amount sufficient to obtain a standard dyeing of 1/3 S.l. (Standard Intensity), 2 g/l sodium dihydrogen phosphate, 0,3 g/l disodium hydrogen phosphate, and 2% by weight of the substrate of tallow fatty amino-propylene-amine ethoxylated with an average of 100-120 mols of ethylene oxide.

The dyebath is then heated from 40 to 1 000C at a rate of 1 OC/min. The dye concentration in the dyebath is determined spectrophotometrically every 5 min (or 2.5 min when the dye buiids up quickly) and calculated with a computer. The K'pH6-value of the dye to be tested is then calculated according to the method indicated by Atherton E., Downey D. A. and Peters R. H. in J.S.D.C. 74, 242 (1958).

In step (A), the substrate is locally treated, in controlled form or at random, with a liquor or a paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a KIPH6- value > 5. The affinity of the amine for anionic dyes with a K'pH6 > 5 may be assessed e.g. by the following test method: Two dye solutions are prepared a) 0.2 ml of an aqueous solution of a standard anionic dye (1 part dye per 100 parts water), having a K'pH6-value > 5 are added to a 5 ml of demineralized water.

b) A solution is prepared according to a) and then 0.5 ml of an aqueous solution of the alkoxylated fatty amine or polyamine to be tested (0.4 parts amine per 100 parts water) are added to the solution.

A drop of each solution a) and b) is deposited on a thin layer chromatography plate. After drying at room temperature, the spot of the solution a) is coloured on the whole diffusion surface whereas the spot of the solution b) containing the amine having affinity for anionic dyes with a K'pH6-value > 5 is coloured in the center and comprises a substantially colourless and relatively wide diffusion edge.

The amines used in step (A) are compounds known as having levelling or stripping properties. In the following discussion, the alkoxylated fatty amines or polyamines are referred to as reserving agents since it has been found that they give reserve effects. These compounds are free from fibre-reactive groups. Preferably the reserving agent has a cationic or amphoteric character, more preferably cationic.

Preferred cationic reserving agents according to the invention are those of formula I

wherein P is (C1024)alkyl or (C10~24)alkenyl X1 is -CO- or a direct bond in each (AO)x, (AO)v and (AO)z chain A is, independently, -CH2CH2- or

each n is, independently, 2 or 3 m is O or an integer from 1 to 6, and each x, y or z is a numeral from 1 to 100 the sum x+y+z being from 10 to 100, in the form of a free base, acid addition salt, quaternary ammonium salt or mixture thereof, and mixtures of such compounds differing from one another by virtue of the significance of R.

R is preferably (C,2~24)alkyl or (C,2~24) alkenyl. R may be for example dodecyl, hexadecyl, octadecyl, octadecadienyl, arachinyl, behenyl, the mixture of alkyl groups present in soya fatty acid or tallow fatty acid, etc....

n is preferably 2 when m exceeds 1, and preferably 3 when m is 1.

m is preferably 1,2 or 3, more preferably 1.

Preferably the sum x+y+z corresponding to the total number of ethylene-oxy-units, propyleneoxy units or mixture thereof is from 1 5 to 80, more preferably from 30 to 40. The (AO)x y z chains are preferably made up of ethylene-oxy units or ethylene-oxy and propylene-oxy blocks, more preferably of ethylene-oxy units.

The alkoxylated amine or polyamine, particularly the compounds of formula I, may be used in the form of an acid addition salt, quaternary ammonium salt or mixtures thereof. Preferred acid addition salt forms are those derived from hydrogen haloacids, for example from hydrochloric acid. Preferred quaternary ammonium salt forms are those bearing on the quaternized nitrogen atom a (C1~4)alkyl or aryl-(C,~4)alkyl group, especially methyl or benzyl. Suitable anions of the quaternary ammonium salts are e.g. halogenide, preferably chloride, or sulfate ions.

A preferred class of reserving agents of formula I is the one constituted by compounds of formula la

wherein A, X,, x, y, z and n are as defined above, and R' is (C,2~24)alkyl or (C,2~24)alkenyl in the form of a free base, acid addition salt, quaternary ammonium salt or mixture thereof.

Particularly preferred compounds of formula I are amino-propyl-tallow-amine or tallow fatty acid amido-propylamine each ethoxylated with 1 5 to 80 mols of ethylene oxide, more preferably with 30 to 40 mols of ethylene oxide.

The compounds of formula I are either known or may be prepared in known manner e.g. as disclosed in US Patents 3,627,475 and 2,967,755 and in GB Patent 1,006,787.

The amount of reserving agent in the paste or liquor used in step (A) may vary within wide limits depending on the desired effect and on the dyes used. In general, satisfactory results are obtained when the liquor or paste contains 1 to 1 5 g/liter, preferably 1 to 12, more preferably 6 to 10 g/liter of reserving agent.

The paste or liquor applied in step (A) may be alkaline, neutral, or slightly acid provided that the pH of the locally applied liquor or paste is at least one unit higher than the pH of the liquor used in step (B). It is preferably adjusted to an alkaline pH, more preferably to a pH from 7 to 10 depending on the dyestuffs used and the nature of the substrate. Such an adjustment of the pH may be effected by the addition of a basic compound, e.g. trisodium phosphate, disodium hydrogen phosphate, borax etc.

The local application of the reserving agent in step (A) may be effected by known methods, for example by printing, e.g. flat or rotary screen printing or jet printing, space-dyeing or dropping e.g. by the TAK process.

When bi- or multi-coloured effects are desired, the reserving paste or liquor locally applied in step (A) may contain, in addition to the reserving agent, also an anionic dye, a disperse dye or a mixture thereof or an anionic optical brightening agent, provided that the anionic dye or anionic optical brightening agent has a K' H6-vaiue < 5 which is at least one unit lower than the K'pH6-value of the anionic dye used in step (Bp. Depending on the final pattern which is desired, it may be possible to apply one or more of such pastes or liquors, either simultaneously or one after the other.For example, a paste containing the reserving agent alone and one or more liquors or pastes comprising the reserving agent together with a disperse dye or one or more anionic dyes of the specified type may be applied locally in step (A).

Suitable dyes or optical brightening agents for the local colouration are those whose build-up or fixation behaviour is not adversely affected either by the reserving agent or the application conditions.

Suitable anionic dyes include those having preferably a K' pHe-value < 5, more preferably 2 to 6 units lower than the K'pH6-value of the anionic dye applied in step (B). Preferred anionic dyes of this type are non metallized acid and direct dyes containing no more than one sulpho group and metal complex dyes free from sulpho groups, more preferably acid dyes, particularly levelling dyes. Such anionic dyes and the disperse dyes which may be used are known from the Colour Index. Anionic dyes are preferred for the local colouration. Examples of preferred anionic dyes include C.l. Acid Yellow 196, 151, Orange 156, 127, 67, Blue 288, 106, 230, 280, 113, 40, 278, Red 299,336, 401, 57, Green 28, and e.g. C.I.

Direct Yellow 132.

When an optical brightener is applied, preferred brighteners are those having "dyeing" and combinability properties analogous to the anionic dyes used in step (A).

In addition to the reserving agent and optionally the dye or brightener, the reserving paste or liquor may contain conventional additives, for example thickeners. Such thickeners must be resistant to alkaline conditions when an alkaline liquor or paste is used in step (A). Suitable thickeners for the alkaline reserving paste or liquor are e.g. alginates and etherified flour thickeners, especially when the alkali is trisodium phosphate. Preferably the reserving paste or liquor of step (A) has a higher viscosity than the impregnation liquor of step (B). The latter has preferably a viscosity which enables a good impregnation of the substrate whereas the former is preferably thickened to prevent or control its spreading.The viscosity of the reserving liquor or paste of step (A) depends on the application techniques and the desired pattern; for example, it may be about 200 cps in the TAK process or exceed 2000 cps when the liquor or paste of step (A) is applied by printing.

Step (B) is a ground dyeing or printing of the substrate, preferably on the whole area. The expression "ground dyeing or printing" refers only to the application of the dye onto the substrate but does not include the fixation of the dye. Step (B) may be carried out at room temperature according to known methods, e.g. padding, pouring, slop-padding, printing, etc. Suitable anionic dyes for the ground dyeing or printing are those having a K'pH6-value > 5, preferably > 6. Preferred anionic dyes are acid dyes containing two or more sulpho groups and metal complex dyes containing at least one sulpho group. More preferred anionic dyes are 1:2 or 1:1 chromium or cobalt complexes, particularly of azo or azomethine dye, containing one or two sulpho groups. Such dyes are known from the Colour Index.

Particularly preferred anionic dyes include e.g. C.I. Acid Yellow 235, 21 8, Acid Orange 168, Acid Red 399,263, 128, Acid Violet 128, Acid Blue 296, 247, 80, Acid Green 106, Acid Brown 289, 298, 363, Acid Black 21 8.

In addition to the anionic dye, the dyeing liquor used in step (B) may contain conventional additives such as a thickening agent, a dispering agent, a buffer, etc. The dying liquor is adjusted to an acid pH, preferably 4 to 7, more preferably 5 to 6.5. Suitable buffer systems are e.g. an acetic acid/sodium acetate mixture, monosodium phosphate or a mixture of mono- and disodium phosphate.

The pick-up of the dyeing liquor in step (B) is generally in the range of from 60 to 400%, preferably 80 to 200%, based on the weight of the dry substrate.

As it will be appreciated the reserving paste or liquor of step (A) as well as the impregnation liquor of step (B) is free from reducing agents, e.g. hydrosulphites.

Steps (A) and (B) are carried out without any intermediary rinsing or drying step.

Subsequent to the latter of steps (A) and (B), the substrate is submitted to a heat treatment to effect fixation of the dye applied in step (B) and optionally in step (A) or, if used, of the brightening agent. Fixation can be achieved by known methods depending on the dyestuff or agent used, preferably with saturated steam at a temperature from 100 to 1 050C. The heat treatment in step (C) is carried out for 2 to 20, preferably 5 to 10 minutes.

After fixation has been achieved, the substrate may be rinsed and dried in conventional manner.

The substrates dyeable with anionic dyes are preferably those consisting of or comprising natural polyamide, e.g. wool or silk, synthetic polyamide, e.g. nylon 6, 66, etc... and blends thereof, including differential synthetic polyamide (deep dye, medium affinity, and low affinity fibres). The substrate may for example be in form of yarn, fibres, filaments, woven or knitted goods, felt or carpets. The process of the invention is particularly suitable for dyeing polyamide carpets, preferably synthetic polyamide carpets.

The dyeing process of the invention is a continuous dyeing of a substrate according to a wet-onwet method. White, tone-in-tone or coloured effects with soft outlines and more particularly with a total reserve effect on a base dyeing can thereby be achieved. The dyeing process of the invention is also economical as there is no intermediary rinsing, washing or drying step between the steps (A) and (B). This is particularly advantageous for the dyeing of substrates such as carpets, enabling thereby important savings in chemicals, energy and water.

The following Examples further serve to iliustrate the invention. In the Examples all parts are by weight and all temperatures are in degrees Centigrade unless otherwise stated.

The K'pH6-values indicated in the following Examples have been assessed in the presence of the ethoxylated cationic levelling agent Qf Example 1 of US Patent 2,967,755.

Example 1 A nylon carpet is padded to a pick up of 60% with an aqueous liquor containing, per 1000 parts, 5 parts of a commercially available wetting agent based on an ethoxylated higher alcohol and 1 part of a commercially available thickening agent (guar gum). The resulting carpet is then printed on a flatbed printer with two pastes having the following composition per 1000 parts: K'PH6 Paste I Paste lI dyestuff C.l. Acid Yellow 1 51 3-3.5 0.075 part 0.06 part dyestuffC.l.Acid Red 217 4.5 0.05 part 0.17 part dyestuff C.l.Acid Blue 288 2.5 0.30 part 0.02 part tallow-aminopropylamine ethoxy- 10 parts 10 parts lated with 30 mols ethylene oxide commercially available wetting 1 part 1 part agent based on an ethylene-oxide/ propylene oxide addition product commercially available 8 parts 8 parts thickening agent trisodium phosphate 1,5 parts 1,5 parts Each paste has a pH from 7.5 to 8.0.

The carpet is then locally treated on a multitak machine with a colorless paste containing, per 1000 parts: 1 0 parts of tallow-aminopropylamine ethoxylated with 30 mols ethylene oxide 1 part of a commercially available wetting agent based on an ethylene oxide/propylene oxide addition product 8 parts of a commercially available thickening agent, and 1,5 parts of trisodium phosphate The pH of the paste is from 7.5 to 8.0.

Subsequently, the carpet is impregnated on a Kuster machien to a pick up of 400% with a dyeing liquor having the following composition (based on 1000 parts): 0.025 part of dyestuff C.l. Acid Yellow 235 (K'pHe=6) 1 part of dyestuff C.l. Acid Blue 296 (K'pH6=7) 1 part of a commercially available thickening agent, 1 part of a commercially available wetting agent based on an ethoxylated higher alcohol, and monosodium phosphate so that the liquor has a pH from 5.5 to 6.0.

The resulting carpet is finally steamed for 6 minutes at 1 000C in a horizontal steamer.

Example 2 A tufted carpet of polyamide 66 is treated with drops of a liquor containing, per 1000 parts 1 5 parts commercial thickening agent which is alkali resistant 6 parts ethoxylated tallow-aminopropylamine (containing 30 ethylene-oxy units) 2 parts trisodium phosphate, and 977 parts water.

The treated carpet is subsequently impregnated with a padding liquor containing, per 1000 parts 6 parts dyestuff C.l. Acid Brown 298 (K'p6value=6) 8 parts commercial thickening agent based on locust bean flour 1 part commercially available non-ionic dispersing agent based on aromatic polyglycol ether 1 part sodium acetate, and 984 parts water at a pick up of 200%. The pH of this padding liquor has been adjusted to 5 by addition of acetic acid.

The carpet is treated afterwards for 10 minutes in saturated stream at 1000 and then rinsed. A brown dyed carpet with a white pattern is obtained.

Example 3 A tufted polyamide carpet is treated with drops of a liquor containing, per 1000 parts 3 parts dyestuff C.l. Acid Orange 1 56 (K'pH6=2.S) 1 5 parts commercial thickening agent which is alkali resistant 6 parts tallow-aminopropylamine ethoxylated with 30 mols ethylene oxide 2 parts trisodium phosphate, and 974 parts water.

and then padded with a liquor as described in Example 2.

The carpet is subsequently treated for 10 minutes in saturated steam at 1000 and then rinsed.

A brilliant orange soft pattern on a brown background is obtained.

Example 4 Knitted goods of polyamide 6 carpet yarn are printed with a paste containing, per 1000 parts 3 parts dyestuff Acid Blue 40 (K' pH6=value=2) 1 5 parts commercial thickening agent which is alkali resistant 6 parts tallow-aminopropylamine ethoxylated with 30 mols ethylene oxide 2 parts trisodium phosphate, and 974 parts water.

The printed substrate is subsequently impregnated at a pick-up of 100% with a padding liquor as described in Example 2 but replacing 6 parts of dyestuff C.l. Acid Brown 298 by 1 6 parts of dyestuff C.l. Acid Green 106.

The resulting substrate then treated for 10 minutes in saturated steam at 1000.

A print of pure blue shade with soft outlines is obtained.

Example 5 By following the procedure of Example 1, 2, 3 or 4 but replacing the ethoxylated tallowaminopropylamine by the optionally quaternized addition product of 1 mol of a) stearylamino-ethylamine or -propylamine b) behenylamino-ethylamine or-propylamine c) a commercially available amine mixture having the following composition: palmityl-aminopropylamine about 30% stearylaminopropylamine about 30% oleylaminopropylamine about 40% d) N-oleylethylenediamine e) stearamido-propylamine f) tallowamido-propylamine with 1 to 100 mols ethylene oxide and/or 1 to 100 mols propylene oxide (with the proviso that the total sum of ethyleneoxy and/or propylene-oxy units present in the molecule is from 10 to 100), similar good results are obtained.

Example 6 Knitted goods of polyamide 6 carpet yarn are printed on selected areas with a paste containing, per 1000 parts 2.8 parts dyestuff C.l. Acid Yellow 151 (K'pH6-value=3) 2 parts dyestuff C.I. Acid Yellow 127 (K'pH6=-value=3.5) 2.8 parts dyestuff C.l. Acid Orange 127 (K'pH6-value=3.5) 4 parts tallow-aminopropylamine-ethoxylated with 30 mols ethylene oxide 1 5 parts commercial thickening agent which is alkali resistant 1 part tri-sodium phosphate 4 parts di-sodium hydrogeno-phosphate, and 968.4 parts water.

The printed goods are subsequently impregnated with a padding liquor containing, per 1000 parts 1 2 parts dyestuff C.l. Acid Green 106 (K'psvalue=8.5) 4 parts commercial thickening agent based on locust bean flour 2 parts commercially available non-ionic dispersing agent, and 982 parts water at a pick-up of 120%.

The pH of this padding liquor has been adjusted to 6 by addition of acetic acid.

The material is subsequently treated for 10 minutes in saturated steam at 1000 and then rinsed.

Yellow and orange patterns with soft outlines are obtained on a green background.

Example 7 Proceeding in a manner analogous to Example 6 but replacing the mixture of C.l. Acid Yellow 151, C.l. Acid Yellow 127 and C.l. Acid Orange 127 by a mixture of 2 parts of dyestuff C.l. Acid Orange 156 (K'pH6-value=2.5) and 0.4 parts of dyestuff C.I. Acid Blue 40 (K'p6value=2) and for the ground dyeing the 12 parts of dyestuff C.I. Acid Green 106 by a mixture of 2.2 parts of dyestuff C.l. Acid Browr 298, 0.7 parts of dyestuff C.l. Acid Green 106 and 8.24 parts of dyestuff C.I. Acid Blue 80 (K'PH6- value=9), simiiar good results are obtained.

Claims (18)

Claims

1. A process for dyeing an anionic dyeable substrate which process comprises A).applying locally to the substrate at room temperature a liquor or paste containing an alkoxylated fatty amine or polyamine having affinity for anionic dyes with a K'pH6-valuek5, followed by B) impregnating the substrate with an acid dyeing liquor containing an anionic dye having a KtPH6- value > 5, and C) subsequently submitting the substrate to a heat treatment to effect fixation of the dye.

2. A process according to Claim 1, wherein the liquor or paste applied in step A) contains an alkoxylated fatty amine or polyamine of formula I

wherein R is (C,0~24)alkyl or (C10~24)alkenyl X, is -CO- or a direct bond in each (AO)x, (A--O), and (AO)z chain A is, independently, -CH2CH2- or

each n is, independently, 2 or 3 m is O or an integer from 1 to 6, and each x, y or z is a numeral from 1 to 100 thb sum x+y+z being from 10 to 100, in the form of a free base, acid addition salt quaternary ammonium salt or mixture thereof, or mixtures of such compounds differing from one another by virtue of the significance of R.

3. A process according to Claim 2 wherein the liquor or paste applied in step A) contains an alkoxylated fatty amine or polyamine of formula la wherein

A,X1,x, y, z and n are as stated in Claim 2, and R' is (C,2~24)alkyl or (C12'24)alkenyl.

4. A process according to Claim 3, wherein the alkoxylated fatty amine or polyamine is an aminopropyl-tallow-amine or tallow fatty acid amido-propylamine each ethoxylated with 1 5 to 80 mols of ethylene oxide, in the form of a free base, acid addition salt, quaternary ammonium salt or mixture thereof, or mixtures of such compounds differing from one another by virtue of the significance of R'.

5. A process according to any one of the preceding claims wherein the liquor or paste applied in step A) contains 1 to 1 5 g/liter of alkoxylated fatty amine or polyamine.

6. A process according to Claim 5 wherein the liquor or paste applied in step A) contains 1 to 12 g/l of alkoxylated fatty amine or polyamine.

7. A process according to any one of the preceding claims wherein the liquor or paste applied in step A) has a pH from 5 to 10, the pH being at least 1 unit higher than the pH of the liquor used in step B).

8. A process according to any one of the preceding claims wherein the liquor or paste applied in step A) contains, in addition to the alkoxylated fatty amine or polyamine, a disperse or anionic dye or a mixture thereof or an anionic optical brightening agent, provided that the anionic dye or anionic optical brightening agent has a K'pH6-valueA5 which is at least one unit lower than the K'pH6-value of the anionic dye used in step B), and the dye or optical brightening agent applied in step A) is also fixed by the heat treatment of step C).

9. A process according to Claim 8 wherein the liquor or paste applied in step A) contains, in addition to the alkoxylated fatty amine or polyamine, an anionic dye having a K'pH6-value 2 to 6 units lower than the K'pH6-value of the anionic dye applied in step B).

10. A process according to any one of Claims 8 and 9, wherein the anionic dye is a non metallized acid or direct dye containing no more than one sulpho group or a metal complex dye free from sulpho groups.

11. A process according to any one of the preceding claims, wherein step B) is a ground dyeing or printing of the whole area of the substrate.

12. A process according to any one of the preceding claims, wherein the dyeing liquor used in step B) has a pH from 4 to 7.

1 3. A process according to any one of the preceding claims wherein the anionic dye applied in step B) has a K'pH6-value > 6.

14. A process according to Claim 13, wherein the anionic dye is an acid dye containing at least two sulpho groups or a metal complex dye containing at least one sulpho group.

1 5. A process according to any one of the preceding claims, wherein the pick-up of the dyeing liquor in step B) is from 60 to 400%.

16. A process according to any one of the preceding claims, wherein the substrate dyeable with anionic dyes comprises natural or synthetic polyamide or blends thereof.

1 7. A process according to any one of the preceding claims substantially as hereinbefore described with reference to any one of Examples 1 to 7.

18. A dyed substrate whenever obtained by a process according to any one of Claims 1 to 1 7.