CH616441A5 - Process for the preparation of sulphonic acid group-free basic anthraquinone dyestuffs - Google Patents

Abstract

The sulphonic acid group-free basic anthraquinone dyestuffs of the formula <IMAGE> in which F, W, R, R-R3, Y, Q, Z and A<(-)> have the meanings given in the claim, are prepared by reacting a compound of the formula <IMAGE>  (II) with a compound of the formula <IMAGE> in which A denotes a radical which can be converted into an anion A<(-)>. <??>Use of the dyestuffs for dyeing textile material made of polyacrylonitrile, synthetic polyamides or synthetic polyesters, which are modified by acidic groups, and also leather and paper.

Description

The invention relates to a process for the preparation of sulfonic acid group-free basic anthraquinone dyes of the formula

F-W

R R9 © ''

—N-C-Y-O-Q

t Î

R1R3

Z A

z a

a),

45 where

F the remainder of an anthraquinone free of sulfonic acid groups, z 1 or 2,

W is the direct bond or a bridge member and each cationic group has an anionic group, then R is an optionally substituted hydrocarbon group, Ri is an amino or alkoxy group or an optionally substituted hydrocarbon group,

Y is a radical of the formula

where R7

O O

II II

for — S-, —O—, —C—, -S-,

-C-R8 RS

or —N — and Rs

O O

Rs

-CH2 -, - CH-,

55 R4 - (CH) x—,

R4

"0 —CH = CH-CH—,

-C = C — CH— or R4

—CH — R5 — CH — CH—

I I I

R4 R4 R4

65

3rd

616441

R.2, R3 and R4 are each hydrogen or an optionally substituted hydrocarbon radical,

Rs is a hetero atom or a hetero atom group,

A® an anion,

x 1 to 9 and

Q is a residue of the formula

O

O

15

-S-, - SO2- or —C— are available,

wherein Rô is hydrogen or an optionally substituted one

Hydrocarbon residue means.

The remainder A can stand for the acid residue of an ester.

The basic dyes can contain an ammonium, hydrazinium, cycloimmonium or an etherified hydroxylammonium group as cationic groups. The cationic group can be bonded externally to the dye body via a bridge member. In addition to the one cationic group, the dyes can also contain a further cationic group and / or a protonated primary, secondary or tertiary amino group.

The radical Q advantageously represents Qi where Qi is a radical of the formula

where R7

O O

II II

for —S—, —O—, —C — j —S—,

C> / O

Rg

-CH2 - CH-,

XC \

R'8 Rs or —N — and

R8

Rs for an optionally substituted hydrocarbon radical, the aromatic rings Zi to Zs with the exception of water-solubilizing groups and cationic groups can be further substituted and the radicals R and Ri, if Ri stands for an optionally substituted hydrocarbon radical, together with the N® bonded to these radicals -Atom can form a saturated or partially saturated heterocycle, characterized in that a compound of the formula

20th

25th

30th

F-W-N

R

Ri

(H),

with a compound of formula R2

A-C-Y-O-Q (III),

R3

in which A denotes a radical which can be converted into an anion Ae.

The bridge member W advantageously stands for a divalent bridge member and Rs can be —O-, -S-, —N—,

re

)

? a

-GOV- •

40 or an optionally substituted carbazolyl, dibenzothiophenyl, dibenzothiophenyldioxylyl, fluorenyl or fluorenonyl radical, in which

R9 is hydrogen, halogen, nitro, cyano, trihaloalkyl, an optionally substituted alkyl or alkoxy radical, aralkyl radical, a carbanoyl radical, a primary, secondary or tertiary amino group, an acyl radical, for. B. an aroyl radical or an acylamino group, a carbamoyl group, an N-alkyl-carbamoyl group, an N, N-dialkylcarbamoyl group, an N-alkyl-N-arylcarbamoyl group, a sulfamoyl, N-alkyl-50 sulfamoyl, N, N- Dialkylsulfamoylrest, an alkylsulfonyl or arylsulfonyl radical, aralkoxy, aryloxy z. B. naphthoxy radical, a carboxylic acid alkyl or aryl ester radical, an aryloxyalkyl radical or an arylazo radical,

Rio hydrogen or a low molecular weight alkyl radical, ss R11 hydrogen, an optionally substituted alkyl, aryl, alkoxy or aryloxy radical, halogen, -CF3, -NO2, -CN, -CO-R12,

60

65

-C-O-R12,

II

O

-0-C-R12, -S02-R12,

II

O

-S02-N (Rl2) 2, -NH-C-R12

O

616441

4th

-SOz-NH-Riz or -CO-NH-R12,

R12 is an optionally substituted hydrocarbon radical and a is 1, 2 or 3. The symbol a can also stand for a number from 1 to 5 if R9 denotes halogen.

The rest Q is preferably Q2,

wherein Q2 is a radical of the formula

-S02-N (RIS) 2, -NH-C-Ris O

-CO-NH-Ris and Ris represent a low molecular weight alkyl radical s.

The radical Q stands in particular for Q3 in which Q3 is a radical of the formula

1"

15

20th

or

R13 and R14 each represent hydrogen, a low molecular weight alkyl or alkoxy radical, halogen, nitro, cyano, trifluoromethyl, a benzyloxy or phenoxy radical, a group of the formula 35 -CO-R15, or

-C-O-R15-SO2-R15-SO2-NH-R15,

II

O

wherein the aromatic rings Zio and / or Zu with the exception of water-solubilizing groups and cationic and R'i3 are hydrogen, halogen, cyano or the -N02 group.

Particularly good dyes are those in which the radicals R13 and R14 each represent hydrogen, halogen, -CFs, -CN -NO2 or a low molecular weight alkyl or alkoxy radical.

The dyes also correspond to the formula

(XXX),

Y - 0 - Q

Groups may be further substituted; or the formula

NH-CH2-CH- (CH2)

-R.

<-1-

Ji28 n25

CH-Y ^ O-Qg

(XXXI),

5

616441

wherein

Rö7 hydrogen, halogen, a low molecular weight alkyl or alkoxy radical, a phenyl or benzyl radical, Rö8 hydrogen, halogen or cyan and

R'25 is hydrogen or -OH and z is 1 or 2;

or dyes of the formula

(XXXII),

0 »» -o? 7,? 27

Y9% - CH-YrO - Q 2 1 1 1 2

R28 R25

wherein Y2 - (CH) -X2 or R25

-0- (CH) -x2

R25 mean

or dyes of the formula or dyes of the formula

wherein Xô is 1 to 4; or dyes of the formula

3rd

0

II

II

0

| 25

27th

(XXXIII),

NH-CH0-CH- (CH0) - CH-Y.-O-Q.

I 2 2 2 I I 1 '

^ ©

R28 R25

0 NH-R

27th

NH-R27

K

25th

R27 ^ 25

-CO-NM- (Cil) - N - CII-Y -0-Qo 1 x6 I 12

R,

NH-R,

28

27th

55

R

0 11

yu - (CH2) X-®N - (CH8) X- 0 -H "71

^ (XXXV),

58

lz

10th

II

0

I.

NH

69 ^ 0

A ©

(XXXIV),

616441

in which gen and

Red represents hydrogen, methyl, ethyl, propyl, butyl, dodecyl, meth- R71 methyl or ethyl;

oxy, ethoxy, benzyloxy or halogen,

R70 is hydrogen, methyl, ethyl, methoxy, ethoxy or halo

or dyes of the formula

(XXXVI),

"58

° - (CH2) x-0N - (CH0) v- 0 - Q

2 I R

71

2 x,

A

©

wherein R72 is hydrogen, methyl, ethyl, propyl, butyl or cyclohexyl;

or dyes of the formula

(XXXVII),

0

38

/ V -— CHo - N - (CHp) - 0 - CU

, e or dyes of the formula or dyes of the formula

II 0

Il70

71

35

(XXXVIII)

"0 - p

58

A

©

4 1

"71

NH-RrC I ^ 5

58

, ^> - C0-NH- (CH2) x -®n - (CHo) v. "0 - Q

V

NH-R,

4!

2 x,

* 71

72

. (XXXIX).

In these formulas, R27 means a low molecular weight alkyl radical, a benzyl, Phe-

R25 is hydrogen, a phenyl radical or a low molecular weight ~ or cyclohexyl radical,

ren alkyl radical, R28 is a low molecular weight alkyl or alkoxy radical or

7

616441

an amino group, Yi a radical of the formula

- (CH2) -xa,

R.26

—CH = CH-CH—,

R26

-C = C-CH- or I

R.26

R.26 R26 R26

R26 is hydrogen or a low molecular weight alkyl radical, Xi 1 to 5,

X21 or 2,

X4 2 to 4,

Xs 2 or 3,

R58 methyl, ethyl, propyl or butyl,

R55 is hydrogen or methyl.

In the cationic compounds, the anion Ae can be exchanged for other anions, e.g. B. with the help of an ion exchanger or by reaction with salts or acids, optionally in several stages, for. B. over the hydroxide or over the bicarbonate. Anion A® means both organic and inorganic ions. B. halogen, such as chloride, bromide or iodide, sulfate, disulfate, methyl sulfate, aminosulfate, perchlorate, carbonate, bicarbonate, phosphate, phosphoromolybdate, phosphorus wolframate, phosphorus tungsten molybdate, and benzenesulfonate -, Naphta-linsulfonat-, 4-chlorobenzenesulfonate, oxalate, maleinate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, malate, methanesulfonate or benzoate ions or complex anions, such as that of double chlorine zinc. The index a mainly stands for a number 1, 2 or 3; however, it can also be a number from 1 to 5 if R9 represents a halogen atom.

Halogen as a substituent is to be understood in particular as chlorine.

Optionally substituted hydrocarbon radicals are in particular optionally substituted alkyl, cycloalkyl, phenyl or naphthyl radicals.

Alkyl, alkenyl or alkenylene radicals can be straight-chain or branched and can contain 1 to 18 or 1 to 12 and preferably 1 to 6 carbon atoms; low molecular weight alkyl radicals usually contain 1 to 4 carbon atoms. Alkoxy radicals probably contain 1, 2 or 3 carbon atoms in the alkyl radical.

If these radicals are substituted, they contain in particular a hydroxyl group, a halogen atom, the cyano or an aryl group. Alkyl can be used for such cases for an aralkyl, e.g. B. are a benzyl radical. Cycloalkyl radicals contain, for example, 5 to 7 carbon atoms and are advantageously cyclohexyl radicals, which can mostly be substituted by alkyl or alkoxy groups or halogen. Aryl radicals mainly represent optionally substituted phenyl radicals; but they can also stand for naphthyl residues. The radicals R and Ri together with the N atoms bonded to these radicals can represent a 5- or 6-membered, saturated or partially saturated heterocycle, that is to say for example a pyrrolidine, piperidine, morpholine or piperazine ring. All residues of aromatic character, e.g. B. aromatic carbocyclic radicals, or heterocyclic radicals, for. B. aromatic heterocyclic radicals can each carry substituents, especially non-water-solubilizing substituents, for. B. halogen atoms, nitro, amino, cyano, rhodane, hydroxyl, alkyl, alkoxy, trifluoroalkyl, trichloroalkyl, phenyl, phenyloxy, alkylamino, dialkylamino, acyl, acyloxy, acylamino -, such as B. urethane, alkylsulfonyl, arylsulfonyl, sulfonic acid amide, alkylsulfonic acid amide, dialkylsulfonic acid amide, arylsulfonic acid amide group, aryl-azo, e.g. As phenylazo, diphenylazo, naphthylazo, etc. Divalent bridge members can be optionally substituted alkylene or alkenylene residues with, for example, 1 to 12 or 1 to 6 carbon atoms, these residues being straight-chain or branched or on ring members, such as cyclohexylene or Phenylene radicals or bound to heteroatoms or heteroatom groups or can be interrupted by such, z. B. by

-O-, -S-, -N-, -SO2-N, -N-SO2-,

I I i

R2 R2 R2

—N-CO— or - CO-N—.

I I

R2 R2

The following bridge members are mentioned: - (CH2) -p,

- (CH2) p 0- (CH2) q-,

where p and q represent the number 1 to 6,

-CH2-CH-CH3, -CH2-CHOH-CH2-, -CH2-NH-CO-CH2-,

-CH2-CO NH-CH2-, - (CH2) p-NH- (CH2) q-,

-NH-CH2-CHOH-CH2-, etc.

Protonatable groups are to be understood as meaning those nitrogen-containing radicals which can form salts in an acid medium, in particular a mineral acid medium, with the addition of a proton, and thus make the dye water-soluble.

The new compounds can be converted into coloring preparations. The processing z. B. in stable, liquid or solid dye preparations can be done in a generally known manner, for. B. by grinding or granulating or then by dissolving in suitable solvents, optionally with the addition of an auxiliary z. B. a stabilizer.

Such preparations can be obtained, for example, according to the information in French patents 1,572,030 and 1,581,900.

The new compounds are used for dyeing or printing fibers, threads or textiles made therefrom, which consist of or contain homo- or copolymers of acrylonitrile or as-dicyanoethylene. It is also possible to dye or print synthetic polyamides or synthetic polyesters modified by acidic groups. Such polyamides are known for example from Belgian patent 706 104. Corresponding polyesters are known from US Pat. No. 3,379,723. The compounds are also used to dye plastic materials, leather and paper. Dyeing is particularly advantageous in aqueous, neutral or acidic medium at temperatures from 60 ° C. to boiling temperature or at temperatures above 100 ° C. under pressure.

Level dyeings are obtained which have good light fastness and good wet fastness properties, for example good washing, welding, sublimation, pleating, decaturing, ironing, steam, water, sea water, dry cleaning, overdyeing and solvent fastness; In addition, they have good salt compatibility and are readily soluble, especially in water. Furthermore, the dyes have good fastness to boiling, good pH stability and s

1#

15

2 «

25th

30th

35

40

45

50

55

60

65

616441

8th

reserve z. T. foreign fibers; in addition, they have good cooking temperature stability and are quick-drawing in combination with other basic dyes.

Those compounds which have good solubility in organic solvents are also suitable for coloring natural plastic compositions or dissolved or undissolved plastic, synthetic resin or natural resin compositions. For example, some of the new compounds can be used to dye tannic cotton and regenerated cellulose. It has been shown that mixtures of two or more of the new compounds or mixtures with other cationic dyes can also be used advantageously. The German patent specification 1 719 397 is to be mentioned as state of the art.

In the following examples, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.

Table A (continued)

K4 stands for the rest ch,

-N-C2H4-O nh "

i »ch

! J

Ks stands for the rest -n-c

15

example 1

41.2 parts of 1 - (3'-dimethylamine) -propylamino-4- (4 "-meth-20 yl) -phenylamino-anthraquinone are dissolved in 200 parts of dimethylformamide at 60 ° and in the course of 2 hours with 21 parts 2-phenoxyethyl chloride added at 80 ° C. The resulting dye of the formula

Kö stands for the rest

25 K7 stands for the rest _ •

30th

Eq

©

Ks stands for the rest

35

A / °

is clarified after treatment with a little activated carbon and diluted at 60 ° with 900 parts of brine. The dye <10 suspension is stirred for 20 hours, the dye is filtered off and the moist presscake is washed with 450 parts of 20% brine. The dye is dried in vacuo at 60 °. The water-soluble dye colors «Orion» in greenish blue tones with generally good fastness properties.

K9 stands for the rest of HQ-1

-n \

ch

—Ch n-c.h.-o S 2 4

45

Table A (continued)

K® in formulas (f) to (h) can stand for the symbols Ki® to K46®, where Ki® to K46® mean the following groups:

Kio stands for the rest hc =!

-n

50

Ki stands for the rest -N-C ^ H ^ -O CH_

? 2H5

K2 stands for the rest —N — C ^ H ^ -O1

SH5

©

-c '

ch_

ch n-C2H4 ~ O

ss

©

Kn stands for the rest

"O

/

c2h4 ° h

K3 stands for the rest -N-C „H. -0

2 4 c2h4oh

©

Ki2 stands for the rest

C2H4

? 2H5

-n-c2h4-o C2H5

Table A (continued)

616441

Cl

C "Mr.

V2 "5 / \

K13 stands for the rest -N-C ^ H ^ -O- ^ y— CI ".

Ks

^ 2H5

Km stands for the rest-n-c H ~ 0, 2 4

C2H5

©

©

©

©

C "H.

12 5

Ki7 stands for the rest -N-n H i 2 4

C2H5

^ 2H5

Ki s stands for the rest - ^ - C H

2 4

C2H5

©

©

C_H

2 5

Ki9 stands for the residue -N-C H, -0, 2 4

C2H5

©

K20 stands for the rest

K21 stands for the rest

C2H5

©

©

616441

K22 stands for the rest

10th

Table A (continued)

? 2h5

-fCA-o-

c2h5

K23 stands for the rest

C2%

-fc2H4-0-

c2h5

K24 stands for the rest

? 2H5

-n-c2h4-o

C2H5

K25 stands for the rest

? 2H5 -n-c "h, -on

2 4

C2H5

K26 stands for the rest

? 2h5

-N- (CH2) 3-O

c2h5

K27 stands for the rest

? 2H5

-b- (ch2) 4-o-

C2H5

K28 stands for the rest

? 2H5

-n- (ch0) -0

2 5

c2h5

K29 stands for the rest

? 2h5 -n- (ch „), - 0

2 6

C2H5

? 2H5

K30 stands for the remainder -N- (CH) "0

i 2 * 7

c2h5? 2H5

K31 stands for the residue -N- (CH) o-0

1 2 o c2h5

11

Table A (continued)

K32 stands for the rest

? 2h5

-s- (CH2) 9-O-C2H5

K33 stands for the rest

? 2h5 -n ch-ch.-o

«I 2

c2h5 ch3

K34 stands for the rest

-n-c.h.-o 1 2 * 0-ch "

K35 stands for the rest

K36 stands for the rest

K37 stands for the rest

K38 stands for the rest

K39 stands for the rest

K40 stands for the rest

? 2h5

-n-ch ch = ch-ch -1 ^

c2h5

Î2H5

-n-ch -c = c-ch -0 ì 2 2.

c2h5? 2h5

-N-C2H4- ° -C2H4-0

c2h5? 2h5

-rC2H4-S-C2H4 "0

c2h5? 2H5

-n-c2h4-so-c2h4-c2h5? 2H5

-N-C2H4-S ° 2-C2H4

c2h5

K41 stands for the rest

Ï2H5

-rC2H4 "^ C2H4-0

C2H5 °

616441

12

Table A (continued)

K42 stands for the rest

K43 stands for the rest

K44 stands for the rest

K45 stands for the rest

K46 stands for the rest

? 2H5

-n-c "h, -n-c" h, -0

2 4

Ks

!

ch,

2 4

©

©

©

©

©

Table VI below shows the structural structure of further dyes which can be prepared by the process according to the invention. They correspond to the formula nh-ch2-ch- (ch2) x-k

R15

A

©

(f),

so

S5

wherein R'13 to R'is, K® and X have the meanings given in the table. In another column I, the shade of the color on polyacrylonitrile is given. Anion A® are those listed in the description.

The symbol K® can stand for any of the residues Ki® to K46® listed in Table A. These groups can easily be replaced in any of the individual dyes by another of the groupings Ki® to K46®.

R'14

H

R '«H

X 1

K® K2

R ', 3 -CH3

H

H

1

Kl7

-CH3

H

H

1

K2

H

-OH

1

K2

-CHs

H

H

1

K2

H

H

1

Kl?

H

-OH

1

K2

^ 5} °

: H3

blue blue blue blue greenish blue greenish blue greenish blue

The structural structure of further dyes is given in Table VII below. They can be produced according to the information according to the invention and correspond to the formula

60

Q NH-R '

e y-k®

(g):

13

616441

wherein R'i3, R'i6, Y and K® have the meanings given in the columns. In another column I the shade of the color on polyacrylonitrile is given. Anions A® listed in the description are suitable.

The structural structure of further dyes is given in Table VIII below. They can be produced by the process according to the invention and correspond to the formula

Table VII

E.g.

R ', 3

R'l6

K®

Y

I.

9

H

H

K2

-CTÎ2-

reddish blue

10th

10th

H

H

Kl7

-CH2-

reddish blue

11

H

H

Ki

-0-C2H4-

reddish blue

12

H

H

K2

-0-C2H4-

reddish blue

IS

13

H

H

AI 3

-0-C2H4-

reddish blue

14

-CH3

-CH3

Ki

-CH2-

greenish blue

20th

15

-CH3

-CH3

K2

-CH2-

greenish blue

A0 (h),

* 18 0 & 20

wherein Yi, R'17 to R'20 and K® have the meanings given in the columns. In another column I the shade of the color on polyacrylonitrile is given. Anion A® are those listed in the description.

E.g.

R'l?

R'l8

R'l9

R'20

Yl

K®

I.

16

17th

H H

H H

-NH2 -NH2

-NH-CH3

-""O

-CO-NH-C2H4 - O-C2H4-

K2 K2

greenish blue, bluish purple

18th

-OH

-NH2

-NH2

-OH

K2

blue

19th

H

H

-NH2

-NH-CH3

—CO — NH — C2H4—

Ke greenish blue

Staining instructions A ss

20 parts of the dye salt described in Example 1 and 80 parts of dextrin are ground in a powder mill for 4 hours. The same dye mixture can also be obtained by pasting in 100 parts of water and then spray drying. 1 part of the preparation 60 thus obtained is pasted with 1 part of 40% acetic acid, the slurry is poured over with 200 parts of demineralized water and briefly boiled. It is diluted with 7000 parts of demineralized water, 2 parts of glacial acetic acid are added and 100 ° of polyacrylonitrile fabric is added to the bath at 60 °. The 65 material can be pretreated for 10-15 minutes at 60 ° in a bath consisting of 8000 parts water and 2 parts glacial acetic acid.

The mixture is heated to 98-100 ° within 30 minutes, boiled for 1½ hours and rinsed. A greenish-blue coloration is obtained with good light fastness and good wet fastness properties.

10 parts of the dye mentioned in Example 1 is dissolved in 60 parts of glacial acetic acid and 30 parts of water. A stable concentrated solution of the dye with a dye content of about 10% is obtained, which can be used for dyeing polyacrylonitrile in accordance with the above dyeing instructions.

Dyeing Instructions B 20 parts of the dye from Example 1 are mixed with 80 parts of dextrin in a ball mill for 48 hours; 1 part of the preparation thus obtained is 40% with 1 part

616 441

14

Pasted acetic acid, pour over 200 parts of demineralized water and boiled briefly. This stock solution is used for staining as follows:

a) Diluted with 7000 parts of demineralized water, 21 parts of calcined sodium sulfate, 14 parts of ammonium sulfate, 14 parts of formic acid and 15 parts of a carrier based on reaction products of ethylene oxide

Dichlorophenols and enters the bath at 60 ° with 100 parts of polyester fabric modified by acidic groups. The material can be pretreated for 10-15 minutes at 60 ° in a bath consisting of 8000 parts water and 2 parts glacial acetic acid.

b) The mixture is heated to 98-100 ° within 30 minutes, boiled for one hour and rinsed. A level green-tinted-blue coloration with good wet fastness properties is obtained.

Example 21

NH-CH,

u3

: h ~ (ch2) 3 ~ n <^> c2h4 ~ 0 CH "

Cl

0

Example 22

B

Claims (2)

616441 2nd PATENT CLAIMS 1. Process for the preparation of basic anthraquinone dyes of the formula free from sulfonic acid groups F-W - \ R R © '' —N-C-Y-O-Q i t R1R3 © (I), Rs for an optionally substituted hydrocarbon radical, the aromatic rings Zi to Zs can be further substituted, with the exception of water-solubilizing groups and cationic groups, and the radicals R and Ri, when Ri represents an optionally substituted hydrocarbon radical, together with the N® atom bonded to these radicals a saturated one or can form partially saturated heterocycle, characterized in that a compound of the formula R wherein F the remainder of an anthraquinone free of sulfonic acid groups, 15 z 1 or 2, W is the direct bond or a bridge member and each cationic group has an anionic group, R is an optionally substituted hydrocarbon radical, Ri is an amino or alkoxy group or an optionally substituted hydrocarbon radical, Y is a residue of the formula R4 I. - (CH) * -, R4 I. —CH = CH — CH—, —C = C-CH— or -CH-Rs-CH-CH-, I I I! R4 R4 R4 R4 R2, R3 and R4 are each hydrogen or an optionally substituted hydrocarbon radical, R5 is a hetero atom or a hetero atom group, A® an anion, x 1 to 9 Q is a radical of the formula or 35 F-W-N (II), Ri with a compound of formula R2 A-C-Y-O-Q (III), Rs 25th in which A denotes a radical which can be converted into an anion A®. 2. A process for mass dyeing plastics or for dyeing leather with dyes of the formula (I), obtained by the process according to claim 1.