GB Patent 971358 - Dyeing,printing and/or fluorescent brightening of textile materials and compositions for the same

Description

PATENT SPECIFICATION

0 X aft NO DRAWINGS 971358 4,ftf S si Date of Application and filing Complete Specification: March 8, 1963.

No 9239/63.

Application made in Germany (No B 66298 I Vc/8 m) on March 10, 1962.

Complete Specification Published: Sept 30, 1964.

f"ig) Crown Copyright 1964.

Index at acceptance:-D 1 B( 2 B 1 C, 2 B 1 E, 2 82 D, 2 C 1 A 5, 2 C 1 A 8, 2 C 2 B, 2 C 2 F, 2 D, 2 F, 2 K 2 A, 2 K 2 B 4, 2 K 2 B 6, 2 L 1, 2 L 2, 2 L 3, 2 L 5 A, 2 L 5 D, 2 R); D 1 P( 1 A 4, ICIA, 1 C 2 A, 1 C 2 B, 1 C 3 A, 1 C 3 D, 1 C 4, 1 D) International Classification:-D 06 p (D 061) The inventors of this invention in the sense of being the actual devisers thereof within the meaning of Section 16 of the Patents Act 1949 are: WALTER GROSCH, a citizen of Austria, GERHARD LUETZEL and WERNEMR ROHLAND, citizens of Germany, residing, respectively, at 4 a Rene-Bohn-Strasse, Ludwigshafen/Rhein, Germany; 7 Liebermannstrasse, Ludwigshafen/Rhein, Germany; and 23 Pfalzgrafenstrasse, Ludwigshafen/Rhein, Germany.

COMPLETE SPECIFICATION

Dyeing, Printing and/or Fluorescent Brightening of Textile Materials, and Compositions for the same We, BADISCHE ANILIN & SODA-FABRIK AKTIENGESELLSCHAFT, a German Joint Stock Company, of Ludwigshafen/Rhein, 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 decribed in and by the following statement:-

This invention relates to a process for the dyeing, printing and/or fluorescent brightening of textile materials in which the material, preferably in the presence of agents having an alkaline reaction, is treated, if necessary at elevated temperature, with a dye or fluorescent brightening agent which contains at least one reactive hydrogen atom attached preferably via nitrogen, oxygen or sulphur, or which is capable of forming one or more such hydrogen atoms during the process and with a heterocyclic compound substituted by at least three epoxy groups or by two epoxy groups and at least one CH 2 = CH-COgroup or a group convertible into the same during the course of the process.

The invention also relates to compositions for the dyeing, printing and/or fluorescent brightening of textile materials which compositions contain a dye or fluorescent brightening agent which contains at least one reactive hydrogen atom preferably attached via nitrogen, oxygen or sulphur, or which is capable of forming one or more such hydrogen atoms during the process and which also contain a heterocyclic compound substituted by at least three epoxy groups or by two epoxy groups and at least one lPrice CH 2 = CH-COgroup or a group convertible into such a group during the process, and which if desired also contain a substance having an alkaline reaction, a dispersing agent and/or a protective colloid and/or one or more dyeing and/or printing auxiliaries.

It is known from British Patent Specification No 869,549 that material containing hydroxyl groups, for example cellulosic textile material, can be dyed by treating it with dyes which contain reactive amino groups and with a polyepoxide Only diepoxides, particularly butadiene diepoxide, are specified as polyepoxides.

With these dyeing methods, for which a relatively large amount of the said reactive additives is required with reference to the amount of dye used, onlyr an unsatisfactory degree of fixation is achieved, i e dyeings are obtained by these methods in which the difference in colour strength between an unsoaped sample and a soaped sample is quite considerable.

Furthermore the process described in British Patent Specification No 869,549 is greatly limited in its use by the marked irritant effect which butadiene diepoxide has on the eyes.

We have now found that textile material, such as fibres, filaments, threads, flock, woven fabrics and knitted fabrics can be dyed, printed and/or optically brightened wash-fast shades by the process according to this invention.

The process according to this invention is particularly suitable for the dyeing, printing and/or fluorescent brightening of material containing hydroxyl groups, i e textile material of native and/or regenerated cellulose or of polyvinyl alcohol It may however also be used for textile material of cellulose esters, polyacrylonitrile or copolymers of acrylonitrile with other vinyl compounds or for textile material of linear polyesters, for example of polyethylene glycol terephthalate or of products based on terephthalic acid and p-dimethylolcyclohexane; it may also be used for textile material of natural and/or synthetic substances containing carboxylic amide groups, such as wool, natural silk or linear polyamides.

In the following description, the word "dyes" is intended to include not only azo dyes, such as monoazo dyes, disazo dyes cr polyazo dyes, metal complex dyes, anthraquinone dyes, azomethine dyes, triphenyl methane dyes, oxazine dyes, dioxazine dyes, or tetrazaporphin dyes, such as phthalocyanine dyes, but also so-called fluorescent brighteners, for example fluorescent compounds of the stilbene, benzimidazole, benzoxazole or benzthiazole series Mixtures of two or more dyes may also be used according to this invention.

The dyes of the abovementioned types contain one or more reactive hydrogen atoms preferably attached via nitrogen, oxygen and/or sulphur, for example in the form of primary or secondary amino groups, -NHgroups in heterocyclic combination, sulphonamide groups, sulphonic alkylamide groups, such as those-having low molecular weight alkyl radicals, sulphonic arylamide groups, such as sulphonic anilide groups, carboxylic amide groups, carboxylic alkylamide groups, such as those having low molecular weight alkyl radicals, hydroxyl groups and/or sulphhydryl groups Those dyes are of particular technical interest which contain one or more reactive hydrogen atoms in the form of HO alkylene groups, H 2 N alkylene groups and/or sulphonic alkylamide groups preferably with low molecular weight alkylene groups or alkyl groups, for example dyes having H 2 N-SO 2 groups, HO-CH-CH 2 groups, H 2 N-CH 2-CH 2 groups, HOCH 2-CH 2-NH-SO groups and/or H'C-NH-SO 02 groups.

Dyes are also suitable for the process according to this invention which contain one or more reactive hydrogen atoms attached via carbon, for example the dye having the formula:0 II l 1.Lc 4 3 t I H 2 CM 3 A "N C -C 14 which is obtainable according to British Patent Specification No 811,221 Dyes which are capable of forming one or more reactive hydrogen atoms preferably attached 65 via nitrogen, oxygen or sulphur during the dyeing and/or printing process are for example dyes containing methylene ether groups or methylene ester groups These groups are converted to methylol groups during the pro 70 cess.

The expression "dyes having one or more reactive hydrogen atoms" is intended to mean that the dyes of this type have one or more active hydrogen atoms which make the 75 dyes capable of reacting after the manner of the so-called Michael addition.

The new process may be used with dyes which are free from watersolubilising groups and also with water-soluble dyes The latter 80 dyes contain as a rule one or more sulphonic acid groups and/or carboxylic groups as watersolubilising groups It is advantageous to use dyes which contain one or more sulphonic alkylamide groups, such as sulphonic 85 acid-( 3-hydroxyethyl)-amide groups or sulphonic acid methylamide groups, as watersolubilising groups, for the process according to this invention The dyes used may be substantive dyes, but may also be so-called 90 reactive dyes which are capable of entering into chemical combination with the material to be dyed and/or printed In the case of substantive dyes, the new process effects an improvement in the fastness properties of the 95 dyeings and prints, and in the case of reactive dyes the proportion of dye fixed on the material to be dyed washfast shades is increased and consequently the yield of the reactive dyes is considerably improved 100 Alkaline-reacting agents are for example inorganic compounds, such as alkali metal hydroxides or alkali metal salts of weak acids, such as sodium carbonate, sodium hydrogen carbonate, sodium acetate, disodium 105 phosphate or trisodium phosphate; organic compounds, such as pyridine or trimethylbenzyl-ammonium hydroxide may however also be used.

The heterocyclic compounds which are 110 substituted by at least three epoxy groups or by two epoxy groups and at least one CHI-=CH-CO group or by groups convertible into such groups during the dyeing or printing process are preferably compounds 115 of the general formula I:971,358 971,358 I,, 1 vt,C-eu Wz-UO-:X � C N 2-CM 2 0.

Ns y_-e 4 -1 O --Cto o O In the said formula, X denotes an organic radical containing an epoxy group or a group convertible into an epoxy group, and Y denotes a X-O-CH 2,-CH 2 radical or the CH 2,=CH radical or a radical convertible into one of these radicals.

Radicals which contain halohydrin groups of the general formula I I -C-cI I OH Hal are examples of radicals convertible into an epoxy group.

Examples of groups convertible into the CH 2 =CH-CO radical are /3-chloropropionyl groups or quaternary groups of the formula:

l-CO-CH 2-CH 2,-NSl Hale I Moreover there may be used the polyepoxy triazine or polyhalohydrin triazine compounds which are described in British Patent Specifications Nos 628,821 and 768,470 as well as in U S Patent Specification No 2,809,942.

Compounds having the general formula I may be obtained for example by the process described in the British Patent Specification

No 900,372 by adding on suitable alcohols to the double linkages of hexahydro-l,3,5-triacryloyl-5-triazine Such suitable alcohols include glycerin-z-mcnochlorohydrin, glycerin1, monochlorohydrin, x methylglycerin-%monochlorohydrin, Y 3-methylglycerin-%-monochlorohydrin and 2,3-epoxypropanol.

Fixation of the dye on the material being dyed is possible even at room temperature, i e.

at about 15 to 30 C, by the new process.

It is advantageous to fix the dyes in the usual way, however, for example by steaming or dry heating at temperatures between 301 and 200 C, preferably between 40 and 150 C, provided the material to be dyed and/or printed permits the use of these temperatures It is advantageous to fix the dyes on cellulosic textile material by steaming or dry heating at '0 to 150 C In this temperature range, fixation of the dyes is as a rule finished within about five to ten minutes.

The process according to the invention may be carried out by treating the material to be dyed and/or printed with the alkaline-reacting agents, the dyes and the reactive additives of 50 the abovementioned kind consecutively in any sequence It is however preferable to treat the material to be dyed with dye liquors or printing pastes containing the alkaline reacting agent, the dye and the reactive additive of the 55 abovementioned kind, and the reactive additive may if desired be prepared in the dye liquor or printing paste The material thus treated is then rinsed in the conventional way, soaped if necessary and finished off It may be of interest 60 to start from dye preparations which contain not only the dyes but also the reactive additives of the abovementioned type, if desired together with dispersing agents and/or dyeing or printing auxiliaries 65 The reactive additives of the abovementioned type are advantageously used in aqueous solution They may however also be used together with dispersing agents in finely divided form or as solutions in water-miscible solvents Suit 70 able water-miscible solvents are particularly dialkyl-carboxylic amides, such as dimethylforinmamide or dimethylacetamide, lactams, such as N-methyl-2-pyrrolidone, ethers, such as glycol ethers or tetrahydrofurane, but also alcohols, 75 such as methanol, ethanol or isopropanol, ketones such as acetone and/or organic acids, such as formic acid or acetic acid.

In addition to alkaline-reacting agents, dyes and reactive additives of the said type, the 80 dye liquors and printing plates may also contain the conventional dyeing auxiliaries and printing auxiliaries provided these agents do not react in an undesirable way with the initial materials necessary for the process Examples 85 of such dyeing auxiliaries and/or printing auxiliaries are surface-active compounds, such as alkyl sulphonates, or compounds which prevent migration of the dyes, such as sodium acetate, or agents which improve the solubility go 90 and fixation of the dyes, such as urea, or thickening agents, for example oil-in-water emulsions, tragacanth thickenings, alginates or methyl cellulose.

As a rule the dye liquor and printing paste 95 is applied to the material to be treated by impregnation by means of a padding machine or by printing In the case of cellulosic textile material, it is also possible to carry out simultaneously with the new dyeing and/or printing 100 process a sc-called resin finishing of the material, for example a crease resist finish.

For the new process for dyeing and/or printing textile material it is usual to employ about to 200 parts of an alkaline-reacting agent 105 and about 20 to 400 parts of a reactive additive of the abovementioned type for each 100 parts of dye.

According to the process of this invention it is possible by the use of a relatively small 110 amount of the reactive additives of the said type in the dye liquor, to obtain deep and I washproof dyeings and to achieve dye yields which are unattainable by the process of British Patent Specification No 869,549 although relatively large amounts of reactive additives are used according to the prior process.

The invention is further illustrated by the following Examples in which parts and percentages are by weight unless otherwise stated.

Parts by volume bear the same relation to parts by weight as the litre measured under standard conditions to the kilogram.

EXAMPLE 1

6.7 parts of finely ground sodium hydroxide is added in small portions at room temperature to a mixture consisting of 17 parts of a commercial mixture of a and r-glycerin monochlorohydrin, 15 parts of benzene and 13 parts of hexahydro-1,3,5-triacryloyl-5-triazine while stirring The mixture is then stirred at about C for an hour and advantageously freed from residues by filtration.

The benzene is removed from the solution by distillation under subatmospheric pressure.

The residue is mixed with 250 parts of water and 350 parts of an alginate thickening containing 40 parts of dry substance to 1000 parts.

A mixture obtained by mixing 30 parts of a commercial formulation of a dye having the formula:/ NHCOOCH 3 OCH 3 NN = _ So O z HZ 0/ \ O H 2 No S 5 N= Nt HCO SH 3 Co OCHN parts of urea and 200 parts of warm water is added to the resultant thickening while stirring.

Cotton fabric is printed in the usual way 35 with the printing paste thus prepared The printed material is dried and then steamed for four to eight minutes at 102 C or three to five minutes at 130 C After the usual washing process, a grey print of deep colour and out 4 C standing fastness properties is obtained.

Similar grey prints are obtained when the printed fabric is not steamed for four to eight minutes but when thermofixation is effected by drying for five to ten minutes, and heating 45 to 140 to 160 C or by bringing the print to a temperature of 190 C for thirty seconds to three minutes, the further procedure being as above described.

EXAMPLE 2 50

The procedure of Example 1 is followed but 12 parts of glycerin monochlorohydrin is used instead of 17 parts and 5 parts of ground sodium hydroxide is used instead of 6 7 parts.

A similar grey print having outstanding fast 55 ness properties is obtained.

EXAMPLE 3 parts of the dye of the formula: H CH 3 H 3 to O No_ known by the name Acid Violet 9 (Colour 60 Index, 2nd edition 1956, volume 3, page 3385, C.I No 45,190) and 20 parts of the compound having the formula:I ", O H 24 Zc,-rt 4 o RY =C-4 �H�O-C H 27-C� z 0 O az o obtainable according to Example 1 of British Patent Specification No 900,372 are dissolved in such an amount of water that 1000 parts by volume of solution are obtained This solution is divided into three equal portions These three solutions are adjusted with aqueous sodium carbonate solution or with dilute hydrochloric acid to three different p H values, namely 11, 7 and 5.

Cotton and rayon staple fabrics are impregnated in a padding machine with the dye liquors thus obtained The materials thus dyed are dried and then steamed for five to eight minutes Violet dyeings having good fastness properties are obtained and those which have been obtained with the alkaline and neutral dye liquors show only a slight loss by washing out in the washing process which is then carfied out.

Similar violet dyeings are obtained when the 971,358 I I 971,358 textile materials are dried for five to ten minutes and then heated to 1400 C to 1500 C instead of being steamed for five to eight minutes, the remaining procedure being as above described.

If the textile material impregnated with a neutral dye liquor of the type described is then impregnated with an aqueous solution of an alkaline agent, for example with a solution which contains 20 parts of sodium carbonate in 1000 parts by volume of water and further treated as above described, a violet dyeing having good fastness properties is obtained.

EXAMPLE 4

14 parts of powdered sodium hydroxide is added in small portions within forty-five minutes while stirring to a mixture consisting of 25 parts of hexahydro-1,3,5-triacryloyl-5triazine, 34 parts of glycerin monochlorohydrin and 50 parts of water The mixture is then stirred at a temperature of 350 to 400 C for about an hour.

The mixture thus obtained is stirred into a paste with a solution which contains 20 parts of the dye having the formula: N-N H oor, ct N=N-a _ CH II U Ho Cc N If Il parts of sodium carbonate, 100 parts of urea and 397 parts of water and with 350 parts of a neutral alginate thickening which contains 40 parts of dry substance in 1000 parts.

White cotton fabric is printed with the printing paste thus prepared The printed fabric is dried and steamed for five to eight minutes at 1021 C After the conventional finishing off, a yellow print on a white ground is obtained which has very good fastness properties.

If the dyes given in the following Table are used instead of the yellow dye specified in this Example, and the remaining procedure is followed as described, prints having similar fastness properties are obtained in the shades indicated: TABLE

No.

Diazo Component Coupling component Colour 1 2-aminonaphthalene-4,8 2-phenylindole-5-sulphonic yellow disulphonic acid c acid 2 2-hydroxyl-1-aminobenzene-5 3-methylpyrazolone-( 5)( 1:2 red-orange sulphonamide chromium complex) 3 2,5-dimethoxy-1-aminobenzene 3-methylpyrazolone-( 5)( 1:2 brown cobalt complex) EXAMPLE 5

14 parts of finely powdered sodium hydroxide is added in small portions within fortyfive minutes while stirring to a mixture consisting of 25 parts of hexahydro-1,3,5-triacryloyl S triazine, 34 parts of glycerin monochlorohydrin and 50 parts of water The mixture is then stirred for about an hour at a temperature of 350 to 400 C 20 parts of the dye described in Example 3, 10 parts of 32 % caustic soda solution, 50 parts of sodium sulphate and water are added to the solution obtained, the amount of water being such that 1000 parts by volume of liquor is formed.

Cotton fabric is impregnated with this dye liquor The impregnated textile material is stored in the moist state for several hours (preferably twelve to twenty-four hours) and then washed as usual A violet dyeing having good fastness properties is obtained.

EXAMPLE 6

If 20 parts of one of the dyes specified in the following Tables I and II be used instead of the dyes or dye preparations specified in Examples 1, 2, 3, 4 and 5, the procedure otherwise being the same as in the said Examples, wet-fast dyeings in the shades specified in Tables I and II are obtained on cotton or rayon staple fabrics:TABLE I

The third and fourth columns (C Ip and CI No) give the numbers of the pages and the numbers of the dyes in Colour Index, 2nd edition 1956, volume 3.

Serial No Name of dye CI p CI No Shade 1 Alizarinuranol BB 3506 62510 grey 2 Silk fast grey BB 3076 15715 grey 3 Celliton fast blue green B 3505 62500 blue grey 4 Celliton fast red GG 3017 11210 red Supramin orange R 3100 17770 orange 6 Palatin fast yellow 3 GN 3051 14006 yellow 7 Palatin fast claret BN 3085 16265 claret 8 Palatin fast yellow 5 GN 3115 19065 yellow 9 Anthralan claret B 3093 17065 claret Supramin claret B 3093 17060 red violet 11 Supramin blue R 3092 17055 blue 12 Fast acid violet B 3385 45186 violet 13 Wool fast blue FBL 3379 44510 blue 14 Flavophosphine 3397 46050 orange CI Basic Orange 21 3402 48035 orange 16 CI Fluorescent Brightening Agent 1 3341 40630 white 17 Flavaniline 3400 47025 yellow 18 CI solvent Black 5 3420 50415 black 19 CI Acid Black 2 3420 50420 black Phenylene blue 3407 49400 blue-green 21 CI Direct Blue 107 3431 51315 blue 22 Fuchsine 3355 42510 violet 23 Methylene blue 3434 52015 blue 971,358 TABLE II

Serial No Dye Shade HOP-S NO-C 1 N yellow S,3 H (obtainable by the process of British Patent Specification No 917,764).

2 \violet (tae N n Sp ( N b p S e a S i 4 (obtainable by the process of German Patent Specification No 742,939) brown (obtainable by the process of German Patent Specification No 742,939)

4 C H 2 c->-\ co_ H N red (obtainable by the process of British Patent Specification No 917,764)

971,358 971,358 TABLE II-cont.

Serial No.

Dye Shade f Hc-Ol l N green (obtainable by the process of British Patent Specification No 805,548)

QIN_/HNH 2 6 N NO N Hy I 411 z N H 6 XN' 2 H Oro NH/'$ -violet (obtainable by the process of British Patent Specification No 908,301)

7 jcojc y NH-N\_S) turquoise blue (obtainable from 1-amino-l-aza-4-thiacyclohexane-4,4-dioxide by the process of French Patent Specification No 930,447) o KH 2 8 W S O Ho c OC blue o NH A H 3 O (obtainable by reaction of 1-amino-4-bromoanthraquinone-2-sulphonie acid with 1-amino-2,5-dimethoxyaniline) H NOIS 9 9 N 2 blue-grey o O > (obtained by coupling diazotised 1-hydroxy-2-amino-5-nitrobenzene with 2-hydroxynaphthalene-6-sulphonamide and converting the monoazo dye into the 1:l-chromium complex) g TABLE II-cont.

Serial No Dye Shade II It lcoppr' h thalo�aa, H_ N C-' O turquoise N, CC 2)z blue II It Hz Hz (obtainable from l-(,-aminoethyl)-aza-4-thiacyclohexane-4,4-dioxide by the process of French Patent Specification No 930,447)

0 II 11 lte cea bh 32 iit 3 J'5 D 4 lf)44 Cjf�blue-green (obtainable according to the process of British Patent Specification

811,221) 12 lCoppe phk}alocmntnei-so NH-Cc c Hu� blue (obtainable by the process of British Patent Specification No 520,199)

13 lCoppet phthcycn t} 50 o Nse H; HH) blue (obtainable by the process of British Patent Specification No 520,199)

14 ltoppet h Nhaocrn�-5 00 INCH'COH)4 O blue (obtainable by the process of British Patent Specification No 520,199) ( 50 i j N = NcppeN 53 H 2 green o I I 1 I C 1 -C\ C 4 H (obtainable by the process of British Patent Speifiation No 916,532) (obtainable by the process of British Patent Specification No 916,532)

971; 358 TABLE II-cont.

Serial No Dye Shade o N Hz 16 50 3 " blue a NH-( -NH CW \H-N:H 2 (obtainable by the process of British Patent Specification No 924,258) o i 1 17 Ho H C -CH 2 o violet H 05 50 """ -3 H'HOHC-N N-CH 2 o H Cii (obtainable by the process of British Patent Specification No 900,764)

18 4 l 1 N/ H yellow -C =-, N N-C z-HH o H CH-CH I I HO-HC-N N-CH 2-9 H (obtainable by the process of British Patent Specification No 900,764)

C.

II 0 C 04 NC 19 ( -HN/ \C red "I, -N=N,,-I"-c i OH HO-Rc-N N-CH 2014 ( C/ (obtainable by the process of British Patent Specification No 900,764)

971,358 971,358 TABLE I cont.

Dye Serial No.

Shade OH i %,k/ Nt T-H O Ired C T CH CH SO 3 ' I i Iu 14 N,c/-c" zo H o (obtainable by the process of British Patent Specification No 900,764) o NH 2 X 50 SO 1 H O 21 blue Y O HZCA 6 /CHZ 01 H clt II o 0 (obtainable by the process of British Patent Specification No 900,764)

OR t R N-Cou M (Ct 4;-0 CH 3) j 22 2-=N->, " t H) red (obtainable by the process of British Patent Specification No 942,566)

23 lco 6IC pkhto Locya nne SO N Hz)z blue X% 03 H)a (obtainable by the process of British Patent Specification No 520,199)

24 l 3 2 -dict o>-coppp p tocw Lotyo-nfn e 3-(SO 2 %Nl-Ca HJO H), reddish blue (obtainable by the process of British Patent Specification No 520,199)

Lcriphon IL-teoppe r phtho-Lo-a-nin e 27 D) blue green (obtainable by the process of British Patent Specification No 520,199)

12 971,358 TABLE II-cont.

Serial No Dye Shade 26 tnonophjnLco phbh-o-n H- ' green blue -np en L<s O ar H (obtainable by the process of British Patent Specification No 520,199)

27 Ehoboco H) green L CO 3 H)3 (obtainable by the process of British Patent Specification No 520,199)

O.H 28 lttrrapknj L-copper pth j Locjo N J(pot 2 i CH�c Icj green (SO,3 H)4 (obtainable by the process of British Patent Specification No 520,199) -OH(SOZ-NH<-C 41 CW Hi Co") 29 lc pp karp Loc-onio p blue (obtainable by the process of British Patent Specification No 520,199) ' loppre ktl cj Hz blue , 503 H(obtainable by the process of British Patent Specification No 520,199)

31 ( N 6 turquoise lcoppet phtihtocyacine$ blue (obtainable by the process of British Patent Specification No 827,568)

971,358 13 TABLE II-cont.

Dye 50314 I,&e Ph KQI-Cyar N (s Ow NH N H,)3 C%H Shade turquoise blue (obtainable by the Process of British patent Specification No 827,568) ( 502-NH-CH 2-CH 2-NH 2)2 33 copper phthalocyanine turquoise blue (SO 3 H)2