DE1769205A1 - Dyes - Google Patents

Description

'B.eeohre IVuftg sur patent registration of

Imperial Chemical Industries Ltd ", London, Great Britain ii

concerning

F a r b e.t off e

Priorities »19» April 1967 and September 27, 1967 Great Britain

The invention relates to new dyes and SIOA particular to such new dye, which are valuable in the dyeing of fibers and other materials and for the production of colored polymers ο

According to the invention, new dyes are proposed which contain at least one group of the formula

109840/1663

-XO (W) β CO - O ^ (I)

KKK

contain, wherein Z is a group of Porael -H- or

denotes, in which R is a hydrogen atom or a substituted or non-substituted alkyl, aryl or Artet aUkylresV, R _{1 is} a hydrogen or Balogenatoa or a Alkyl or eiiyCyanreet, Rg, R- and R * each independently a hydrogen or halogen atom or an alkylreet and R ₅ a hydrogen or halogen atom or a hydrocarbon or cyano atom

The substituted or nioht-eubstituted alkyl radicals denoted with R are preferably lower alkyl radicals, such as Methyl, ethyl, propyl and butyl radicals * and they can contain substituents such as hydroxyl and ethoxy groups. as Examples of substituted or unsubstituted aryl radicals, which are denoted by R »may be mentioned» Phenyl, tolyl, chlorophenyl, sulfophenyl, methoryphenyl, Broi ^ phenyl-, Hitrophenyl-, Mledrisallsyleulfonylphenyl-, Stilfonamidophenyl-, H-Ntedrigellcylsulfonanldophenyl-, Aoetanidophenyl and Hydroxyphenylreete. As examples of aralkylreates, which are almost entirely contained in R, are:

109840/1663

Beneyl, nitrobenzyl, Cblorbenayl and phenylethyl radical

All examples of alkyl radicals, which are indicated by R ,, Rg, B- and E ₄ , selenium especially lower alkyl radicals, never called methyl, ethyl, propyl and butyl radicals »

The hydrocarbon radicals denoted by Rr are in particular lower alkyl radicals, aryl radicals, vie phenyl "and aralkyl radicals such as benzyl .."

Preferably, R ₁ , R ₂ , _{R 1, R 4} and Re each consist of a hydrogen atom.

The dyes according to the invention can have up to four groups of formula I contain »but the dyes are of particular interest, which. one or two such groups im Dye molecule contain

Each of the groups of the formula I is bonded directly to a carbon atom contained in the dye. This carbon atom can form a rope of an aryl radical, which is in the Dye is opposite or it can form one part of an alkyl chain either directly attached to one in the dye

present aryl radical is bonded or to this aryl radical 109840/1663

is bound by a BrUuiumaliOra or a bridging group. Examples of such bridge atoms or groups are -0-, -S-, -NH-, -W-alkyl-, -COHH-, -CON-alkyl-, -SOg-, -SO ₂ NH- and -SO _g N-alkyl-.

The dyes according to the invention, which members of one of the known dye series can be expressed by the following formula:

D - I - - co - c β σ - c m c

R ₁ R ₂ L

in which S, R., R ₂ , R-, Rj. and R- have the meanings given above, D denotes a dye residue and η an integer from one to four i / »t. The dyes are preferably those of the azo series, which can be mono- or polyazo dyes, or those of the nitro, anthraquinone, phthalocyanine or methine series, although they are also those of the diaryl methane, triaryl methanes, xanthea. Can be azine, oxazine or thiazine series. The dyes can contain one or more water-solubilizing groups, such as carboxylic acid, alkyl sulfonic, sulfamyl and, in particular, sulfonic acid groups. If desired, the dyes, in particular those of the azo or phthalocyanine series, can also contain a coordinatively bonded metal, such as, for example, a copper, chromium or cobalt atom.

109840/1663

BATH ORIGINAL

According to another feature of the invention, a method proposed for the production of the specified dyes, which is characterized »that a dye compound which contains at least one group of the formula

- X- H

contains, wherein 2 has the meaning given above, with an Aeylatingmittel is implemented, which is suitable, the rest of the formal

- co - σ s

to introduce ^ where R ₁ »Rg, IU, -R. and R ^ have the meanings given above «

Suitable acylating agents are the anhydrides, esters and in particular halides, such as chlorides, of acids of the formula:

HD-OO-C's 0-0 « Of (II)

wherein R., Rg » R ^» Rx and R ^ have the meanings given above

Examples of acids of the formula II, of which the acylation that can be derived are pentadienes,

109840/1663

4-methylpentadiene, sorbin-, 3-methylsorbin- ,, 5-methylpentadiene-, 5-phenylpentadiene- _s 5 ~ cyanopentadiene-, 2-gyansorbin-, 4-chloropentadiene-, 4-bromopentadiene- and 5 9 5-dichloropentadiene « , uren.

The specified process according to the invention can expediently be carried out in the manner dsJ3 the acid halide or

other acylating agents of a solution or suspension of the dye compound in a suitable reaction medium is added * In the case of dye compounds, which

contain solubilizing one or more solubility in water / group, the acylation may be in water or in a mixture of water with a water soluble organic liquid performed werdenο Bs is common to stir the ßeaktionsmischung, preferably at a temperature between O and 20 ⁰ C ₀ In the In cases where aromatic amino groups are to be acylated, it is usually preferred to keep the acylation mixture at a pH between 6 and 8, but in the case of aliphatic amino groups, pH values of up to the dye containing at least one group may be necessary of the formula I can be isolated by salting it out with sodium chloride and filtering it off

not
Dye compounds which contain one or more water-solubilizing groups can achieve the acylation rank in a suitable organic liquid * such as dicxan or acetone,

109840/1663

EAD ORIGINAL

or in a mixture of a water-soluble organic Liquid carried out with water

Each of the "OOB-G groups present in the dye, is directly attached to a carbon atom of an aryl radical of the dye compounds tied, or any of the -XH grappen is bound to a carbon atom, wel.ch® part of a Forms an alkyl radical which is either directly linked to one of the dye compounds via a bridge or via a

is ' -

Bf'lckengruppe there bound / · Examples of such bridge atoms or groups may be mentioned: -O-, -S- _r -HH- _p - ^ -SO ₀ -, -SO ₂ HH-, -GOKH-, -CON-alkyl - and -

As examples of paraffin compounds which are at least contain an -XH group, where X is a group of Pornel -HR- of the type indicated above denotes that with the acylating agents can be reacted to the dye blinding to get which at least one group of the Formula I, the "compounds of the following classes may be mentioned, without, however, the Eassen being restricted to these mentioned binds

109840/1663

ORIGINAL

Ί ο Monoazo compounds of the ponoel

(I ₁₁ )

where D ^ denotes a mono- or dicyclic aryl radical, which is free from azo and HBR groups > Bie -lHR-Q-group is preferably bound to the 6-7 or 8-8 position of the naphthalene nucleus, with the ITaphthalene nucleus in the 5- or 6-position it also contained a sulfonic acid group *,

D ₁ can be a remainder of the naphthalene ode :? Benaol series .foeseiohnen, which is free of azo substituents, for example a stilbene _v diphenyl ^ benzthiazolylphenyl or biphenylamine radical. In this class, the related dyes are also to be taken into account * in which the -NHR group, instead of being bound to the haphthalene nucleus, is bound to a benzoylamino or anilino group, which itself is in the 6-, 7- or 8-position Naphthalene nucleus is bound "

Particularly valuable paring agents are obtained from those in which D * denotes a sulfonated phenyl or ITaphthyl radical, and in particular of those which have a -SO ^ H group contained in ortho division to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms, such as chlorine, alkyl radicals such as methyl, acylamino groups such as

1098 40/1663

der_ JW ^ _BAD QF ₁₁ Q _1n ^

Acetylamino and alkoxy radicals such as methoxy ».

2 ο Disaaoverbindungen of formula III wherein Dj zeiclmet a bed of azobenzenes, Azonaphtlaalin- or Phenylazonaphthallnreibe dead "and the Naphtlialinkern by NHR and öruppe ggfo through. SuIf on acid as substituted in class 1 »

3 ο Monoazor compounds of Pormel

where D ₁ for an at most dioyclic aryl reet, never
given above, denotes the country where the benzene nucleus may contain further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid and acylamino groups «

The related paraffin compounds are also in this class to take into account in which the -HHR group, instead of dlr »3ct to be bound to the benzene nucleus, to a residual carbon dioxide is bonded, which is bound to the Benaolkern by means of a group of the formula -NR-, where R has the meaning given above «

4 ο mono- or diazo compounds of the formula

1098A n / 166 3rd

KD ₁

wherein D _{1 is} an arylene radical, such as a radical of the azo

benzene, azonaphthalene or phenylaaomphthalin series, or

at most preferably a / dioyclisohen arylene radical of the benzene or

designated Haphthalinreihegv and K the remainder of a haphtholsulfonic acid or an enolated or enolizable ketomethylene bond (for example an acetoacetarylide or a 5-pyrazolone), where the OH group is in o-position to the azo group «a

, jfonaSttre _t a ff—

acid? a 2 — AninonaphtholsulfoneSore or a 2 — Alkylaiaino—

referred to as naphthol sulfonic acids preferably refers to a wheel i kai of

Benzene series containing a sulfonic acid group.

5 β mono- or bisazo compounds of the formula i

D ₁ -H-Bf-K ₂ -HHR (V)

where D ₁ denotes a heat of the _{types specified for D 1} in the above classes 1 and 2 and E ₂ ^{denotes the δθ3} * of an enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) where the -OH group is an adjacent position to the azo group takes _o

6th a The metal complex compounds, for example the copper

and cobalt complementary compounds of dyes of the formulas

109840/1663

XII, 17 - and V (in which D ₁ , K tad Kg have the corresponding meanings given), which contain a metallizable group (for example a hydroxyl, lower alkoxy * or Garboa acid group) in orthostaLlung two azo group in D ₁ »

7ο Anthraohinonverblnchmgon the formula:

0 MBT

- ¥ - HHR
in which the anthraquinone nucleus can contain a sulfonic acid group in the 2-position and, if desired, also in the 5-, 6-, 7- or 8-positions, T is a hydrogen atom or a substituted or non-substituted alkyl radical and V is a bridging group, which may or may not be a bivalent

a best of the benzene series, for example phenylene * or / 4,4 * -s

is valuable stilbene or asobensol residue.

6 »Phi ^ lalooyanine compounds of the formula:

. (SO ₂ - O) _n

1098 40/166 3

where Pc denotes the phthalocyanine nucleus, preferably copper phthalocyanine * G * a hydroxy and / or amino or substituted amino group Q denotes a bridging group, preferably an aliphatic, cycloaliphatic or aromatic bridging group f la denotes a Sah ?, from I to 4 and η a number from Q is 3, provided that η + m in is not greater than 4,>

9ο Nitro dyes of the formula:

NHR B-HH- Β «

HO

where B and B 'denote a monocyclic aryl nucleus and the nitro group in B is ortho to the NH group ₀

10. styryl dyes

wherein A is the residue of a reactive methylene group and

and R- denote alkyl or aralkyl groups _o A, Rg or R- contains at least one NHR group _o

109840/1663

- 13 -

In class 1 . .

6-Amino-1 ~ hydroxy-2- (2 '-aulfophenylazo) naphthalene: iJi * 3 ~ sulfonic acid _t 6-methylainino-1-hydroxy-2- (4' -acetylainino-2 '-sulfophenylaso) -naphthalene-3 -stilf on acid ,

8-Amino-1 ~ hydro3qsr-2- (2'-sulfophenylazo) naphthalene- 3 _} 6-disulfonic acid,

8-Amino-i-hydroxy-2- (4 ^l -chloro-2'-sulfophenylazo) -naphthalene » 3 > 5-distCLfonsäiire,

7-Amino-2- (2'j 5'-disulfophenylazo) -1 «-hydroaqynaphthalene-J-sulfonic acid,

7-methylamino-2- (2 * -sulfophenylazo) -1-hydroxynaphthalene-3-stafonic acid, 7-methylamino-2- (4'-methoxy-2 ^f -sulfophenylazo) -1 hydroxynaphtihalin - ^ - atulfonic acid,

8- (3 '-Aminobenzoylajnino) - 1-hydroxy-2- (2' -sulfophenylazo) -naphthalene-3 - _t 6 = disulfonic acid,

8-Amino * 1-hydroxy-2j 2'-azonaphthalene-1'j 3j 5 '^ 6-te-fcrasulfonic acid, 8-amino-1-hydroxy-2 ^ 2 -azonaphthalene'-1' _} 3j5 '-trisulfonic acid , e-Amino-i-hydroxy ^^ '- azonaphthalene-i' ₅ 3 j5'-trisulfonic acid, 6-Methyland.no-1-hydroxy-252 ^f -azonaphthalin-1 · _} 3,5'-trisulfonic acid,. T-Amino-i-hydrosy ^ 2'-azonaphthalene-1 '^ 3-disulfonic acid, 8-amino-1-hydroxy-2- (4' -hydroacy ^ '-carboxyphenylazo) -naphthalene-3j6 ~ disulfonic acid,
6-amino-1-hydrosy-2- (4'-hydroxy-3'-carboxyphenylazo) -naphthalene-

"= - ■ * 14 -

In class 2

8-Amino-1-nydroacy-2-J4 '- (2 "-sulfophenyiazo) -2 · -mathoxy-5 * -

methylphenylazo7naphthalene ~ 3 - _t 6-distü.f on acid,

8-amino-1-hydroxy-2-pi · '- (4 "-methoxyphenylazo) -2' -carboxyphenyl

aeoj naphthalene-3 ^ -disulfonic acid,

8-Amino-1-hydroxy-2- £ 4 '- (2 "-ΐ33ΓάχΌΧ3Γ-5" j6 ^M -clisulf o-1 "-naphtJayl-

azo) -2 * -carboxyphenylaao / naphthalene-J j6-disulfonic acid _r

4 ^ 4 '-bis (8 ⁿ -Ainino «1" -hydroaty-J "j6 ^M -disulfo-2" ~ naphthyla8o) -

3 3 '-dimetlioxydiplienyl,

6-Amino-1-hydroxy-2- ^ 4 ⁱ - (2 ^H -eulfophenyiazo) -methylphenylajsojnaphthalin-2 j 5-di-sulfonic acid

In KLaaee 5

2- (4'-Amino-2'-methylphenylazo) naphthalene-4 ^ 8-disulfonic acid, 2- (4'-Amino-2'-acetylaminophenylazo) naphthalene-5 j 7-disulfone

acid,

4 ~ Nitro-4 '- (4 - "- methylaminophenylazo) Btilben-2 _y 2 ' -dleulfoic acid

4-nitro-4

2 ^ 2'-dieulfonic acid,

4-Amlno-4 '- (4 ^M -fflethoiyphenylazo) etllben-2 +2 -disulfoxx-acid,

4-Amino-2-inethyla2Oben £ sol-2 ' ₁ 5' -disvtlf on acid , 4-Amino-2 '-hydroxy-5' -methylazobenssol,

4- £ H-Xthyl-N -. (N · -methylaminoethyl) 7 amlno-2 »-chlor-4 ^f -nitro-

azobenzene,

4-fKf-Xthyl-N- (N'-methylaminoethyl) 7 amino-2 -chlor-4'-cyano-

azobensol. 109840 / 1B63

In KLaaee 4

1 - (2 · -> 5 · -Diohlor-4 · -euifophenyl) -3-a »ethyl-4- ( 3" -Mino-4 · -

sulfophenylazo) -5-pyrezolone,

1 - (4 '-Sulfophenyl) "3-carbaxy" 4- (4 "-amino-5 ⁿ -eulioplitiiyla" o)

5-pyrazolone,

1 - (2 · -Methyl-5 ' -salt öphönyl) -5-methyl-4- (4 ^w HSuniiio <-3 ^fl -Henilf0-

phenylaz; o) -5 ~ pyraaoloii, 1 - (2 '-.SuIf ^ ophenyl) -3-iaethyl-4- (3 "-amino-4" -sulfoph

1 - (2 '-Ohlophenyl) -3-ethyl ~ 4- (3 "-aoino-6 ^B « BuXf (»siiweriUeo) -5-

4-Aoino «4 '- (2" ^ hJdTOJQr-? "^" - dleulf0-1 2 ^ 2 «-dleulfoneaur ·» 8-Aoetylamlno-1 -ro3cy ~ 2- (3' -ealno-4 '-sulfohtrv

6-aoetylamino-1-hydroxy

3-sulfcm ^ r ^ ^ _{gg 3} ^ ,, _? . _r - ₅ n ^ 8 s;.

~ 16 -4-Hydroxy ~ 5 - (4 · -ajdLaoj ^ enylazo) -6-ainonaphthalene-2-bilfonic acid,

- (3 ^l -Anlnopheijyl) -5-methyl-4- (2 * ^ 5 '

1 - (2-aminophenyl) -3-oarboxy-4 ~ (2 '- carooxy-4 * -sulf ophenylaao) -

5-pyrazolone,

4-Amlno-4 ^l -j3 "-methyl-4 ^ll - (2"'^ 5 "' -disnlfopbenylazoj-i ^H « pyrajeol

5 ^M -onyljBtilben-2 ^ 2'-disulfona acid,

^η - (2 "· ^ 5 * '-disulfophenylaao) -

In Elasae 6

Bar Eupfer complex of 8-amino-1-hydrory-2- (2 '»hydroxy-5 ^f!

eulfophenylaao) naphthalene-3 _/ 6-disulfonic acid, the Kttpferkonrplex of 6 ~ amino-1-hydroxy-2- (2 '-hydro ^ sr-5' sulfophenylaao) naphthaHn-3-sulfonic acid ₉ the Eupfer complex of 6 -Amino-1-hydro2y-2- (2 ^l ~ hydroxy-5 ^l

the Eupf er complex of 8-Amlno-1-hydroxy-2- (2 ^l -bydroxy-3 ^l -

the Eupf er complex of 6-methylamino-1-hydroxy-2 ~ (2 '-carboxy 5 ' -sulfopnenylaao) naphthalene-3-sulphonic acid , the Eupf er complex of 8-amino ~ 1-hydroxy-2-f4 ⁱ - (2 "-sulfophenylazo) 2 '~ mothoxy-5' naethylphenylasio J-naphthalene-5,6-

dieulfonic acid eρ

10984Π / 1663

Π-,

the copper complex of 6-amino-1-hydroxy-2-pj- ^e ~ (2 "

phenylazo) -2 ⁵ -methoxy-5 * -methylphenylazoJ ~ mphthali2i-3, 5-

disulfonic acid, _: .

the copper complex of 1- (5 ⁱ - ^ äJao «» 4 ^t: --sulfophenyl) ~ 5 - methyl-4 = - | j4 »- (2"'j5" ^f -disulf ophenylazo)» 2 "' - Diethoxy «5" -methylphenylazo] J.

5-pyrazolone _r

the copper complex of 7- (4 '-amino - ^^ sulfoaniline ^ -i -hydroxy-2 - {"4» - (2 " ^! .5" ⁸ -disulfophenylazo) -2 "-metlioxy-5" -metüylphenyl *

azoJnaphthal ^ Ji-5-sulfonic acid,

the copper complex of 6- (4'-amino-? » ⁹ " -Bulfoaniliijci-i-hydroxy-

2- (2! "- carboxyphenylazo) naphtha3.in ~? -Sulfonic acid ₉

the 1 s 2 ~ chroia complex of 7-amino-ii ^f -nitro-1 j 2 '-dihydroxy * 2 j I' - =

azonaphtnalin ~ 3 Jt disulfonic acid '

the 1st; 2-0liromkoniplex of 6-Amino-1 ~ hydroxy-2- (2 ^g -Qarlioxy-

phenylazo) naphthalene-5-ßulfonic acid t,

the 1: 2-Gh2On complex of 8-amino-1-hydroxy-2- (4 ⁱ ~ nitro-2 ^l -

hydroxyphenylazo) naplithalin-3 | 6-dtsulfonic acidQ _t

the 1: 2 cobalt complex of 6- (4'-AmInO-? ¹ -sulfoaniline ^ -1 hydroxy ~ 2- (5 "-chlor-2 ^II -hydroxypher.jrlazo) -naphthalene-3-sulfone-

acid _p

the 1: 2 chromium complex of 1- (5 ^! - Amiiio-4 '- ßulfophenyl)' - 3-nie1; hyl-

4- (2 ^ll -hydro ^ y-4 "-sulf 0-1" -naphthylazo) -5-pyrazolone,

the 1s2-0hxOinfcomplex of 7- (4 '-SuIfoanilino) -1 «-hydroxy ~ 2-

(4 "-amino-2" -carl) oxyphenylazo) nepb.thalene - 3-sulfona acid,

10 98407 166 3

the 1: 2-CbromIoomplj »x van. 1 (T Am

jlaeo) -5-pyra «olon _e

1 -Aoiiio-4- (3 '-eiaiao-4'

acid,

1— ^ t ¹ I t ¹ O -4 — Pl '

(4th

1 -hyaroiyät} 3ylaaino «4 -» (4 '-

»Wnil i nr} -enthmf>h3T> on *

1 -Amino-4 (4 'nae thylaalno-3 * -βηΐ foenJI,, 1 iTpVan1 & raoblnon-2-

1 -fl-Sulfatoftthylaaino-4 -. (4 * «.aal noeni 1.tne) nTrthrR0Trl.Tinno

109840/1663

BATH ORIGINAL

3- (ß-Amlnoäthyl) suitaayl-copper-phthalocyanine-tri - ^ - cniLioiisRure 3- (3 * -Amino-4'-sulfophenyl) milfaii ^ l ~ kupfβr ~ phthalo0yani2l-tri- < 3 — sul £ ons & ure f

Di ~ 4- (3 '-amino-4' -sulfophenyl) eulfamyl-lcupf er-phthalocyaninedi-4-sulfonic acid,
3- (3 * -Aminophenylsulfaayl) -3-sulf acayl-Inqofer-phtlialocyanln-

As examples of . Dye compounds «which at least

defined a «-ZH-flruppe, in which X is a group of the above / formula

is, so that the acylating agents can be reacted to give the dyestuff am, which contain at least one group of the formula I, the following may be mentioned, without, however, the invention being restricted to this.

Azo dyes which contain at least one -SOgHHE group, can in a manner known per se aas diazotizable primary Amines and coupling components are produced, the Amin and / or the EapplTang component together at least one

1098 40/1663

-SOgNHR group contain "" Examples of diazotizable primary amines which contain one or more -SOgNHR-Q groups: i-aminobenzene-2-, 3- or 4-sulfonamide, i-amino-benzene-2-, 3 - or 4-sulfone-N-methylamide, 1-aminobenzenes-; , 1-aminobenzenes, 5-disulfonamid, 1-aminobenaol ~ 2- _f 3- or 4-sulfonahilide, 2-aminophenol-4- ^ or 5-sulfonamid, 2-aminophenol-4- or 5-sulfon-H- methylamide,

2-aminophenca-4- or 5-eulphonanilide, anthranile ^ Jre-5-eulphonamide, 1-AmJLnO-JMtPWhSJLIn- ^ eUIfonamid, 1-amino-2-naphthol- * 4-ETulJTonamid t | nd p-Am ^ yt f ^ ^ i pfi- ^ iii ^ ' H Tn — f —ffl ^ l ' ^ '^' Qff ^ ^ - These primary amines or the corresponding sulfamic acids can be combined with any of the known components, in particular with those of the aoylacetarylamide -, 5-pyrazole, tertiary arylamine, phenol or haphthol compounds. Such coupling components can optionally contain one or more -SO ^ NHR groups. Examples of coupling components which contain one or more -SOjNHH groups are 1-naphthol-3-, 4- or 5-BUlfonaMid, 2-haphthol-3-, 4-, 5- * 6-> 7- or 8- eulfotmmid, 1-haphthol-3,6- or 3,8-dieulfonaaid, 2-haphthol-3,6v. or 6,8-dieulfO2iamid, ii a »id, 1- (2 ^f -3'- or 4 ^l -3ulfaaylphenyl) -3-methyl-5-pyrassolone and acetoacetanilide-4-sulfonaiiid, These coupling components can be diazotized in well known catfish with any

109840/1663

primary amines coupled «earth, including which themselves contain one or more -SOg-NHR groups. Those azo dyes which contain metallizable groups in ortho * position eur azo group * can be in the form of metal complex »can be used, for example, of copper, chroa or cobalt complexes»

Anthraquinone dyes, which at least one

contain 1-amino-4- (2'-, V- or 4 '-sulfamylaniliac ^ - anthraquinone-2-sulfonic acid, i-amino-4- (4'-OhIOr ^ ¹ - or 3 **

8ulfam7lanilinp) anthraquinone ** 2-> sulfonic acid ₉ 1 « mathoxy-2 'or 3 ' ~

1-Amino-4- (2'-methyl-5 · -sulphamylaniline ^ aathraquinone-2-sulphonic acid and 1-amino-4- ( 3 '»5' -disulphaayla2iilino) anthraquinone-2 · ^: aulphonic acids

Phthalooyane dyes which contain at least one -SOg-HHR group are described in detail. Particularly worth mentioning are those dyes in which a copper phthalocyanine nucleus _{contains one to four -SO 2} -NHR groups in the molecule »

According to a further feature of the invention, a modiflsii tea process for the production of the new coloring agents, which asopharyngeal substances represent, the mindeetene an öruppe of

109840/1663

Formula X contain, v.elchcs consists in rttfi a priatfr * · Attift or the corresponding suIfämic acid diaeotiert and the 00 obtained diazo compound coupled with a coupling component ViTd, the primary AwIn and / or the coupling component together containing at least one group of Fozael I

This modified method of the invention can expediently be carried out in such a way that sodium nitrite is added to a solution or suspension of the primary amine, which can be an aoinoazo compound or the corresponding sulfaraic acid, in a dilute aqueous hydrochloric acid solution and the solution or suspension of the diazo compound thus obtained is added to a solution the coupling component is suggested, before the precipitated azo dye is filtered off. If desired, sodium chloride can be added to ensure complete precipitation of the entire amount of the azo dye, which can then be dried, preferably at a temperature below 50 ⁰ O and in a vacuum ·

That used in this modified method of the invention primary AnIn or the corresponding '3ulfaninsSLure know a Be a member of any of the known series of diasotable primary amines, but preferably it is a primary amine

109840/1663

the benzene or ffaphthalene series? which possibly “an arylhBQ- ■ group can contain. The one in this modified procedure The coupling component used in the invention came a link any of the well-known ranges of coupling components your, however, it is preferably a coupling component of the acylacatarylamide, 5-pyraeolone, phenol, naphthol or arylamine ■ rows

Those primary amines or the corresponding sulfamic acids and coupling components which contain at least one group of Formula X can even be folded by the fact that the corresponding primary amine (or sulfamic acid or equivalent ITitroverbindting, which is then reduced) or the Coupling component which contains at least one -XH- (r group, treated with an acylating agent of the type indicated above will «Examples of such connections are:

! J-Pentadienoylamine-caniline-e-sulfonic acid p

N-ethyl-H- (ß-N ¹ -metbyl-N'-pentadienoylaioinoäthyDanilin,

K-ethyl-H- (JH ¹ -methyl-K '-sorboylaminoethyl) aniline,

^ -Amino-K-pentadienoylaniline,

Aniiin-3-sulfon- (N-pentadienoyl-N-methyl) amide,

10984071663

4-chloranil in-3-ßulfon (4'-pentadienoylamino) anilide, 4-ghloran jJ.iii-3-bulfon (B-pentadienoylamino) ethylamide, 4-pentadienoylaininoaniline-2-aulfonic acid, 4-pentadienoylaminoaniline sulf onanilide, 4-pentadienoylaminomethylaniline, aniline-3 ~ 3tLLf on (ß-pentadienoylamino ] ethylamide,

- ~ pentadienoylamine. o) aniXide "

Aniline-5-sulfon (3 '-pentadienoylaiaino) anilide, Anilia-5 ~ sulf <m- (4' -N-pentadienoyl-IT-methylamino) anilide , aniline «2-sulfone- (4 * -H * -pentadienoyl -li '-methylamino) -N-methylanilide ,,

Aniline "2-sulfone- (4'-H'-pentadienoyl-H 'ηβθthylamino) anilid, - (3'-H ¹ -pentadienoyl ~ N * -methylamino) anilid"

Aniline-2-sulf one- (ß-pentadienoylamiiio) ethylamide,

Aniline-2-Bulfon-N-methyl-H- (ß-N'-pentadienoyl-ίί · -metnylamiao) -

ethylamide,

2-chloro-4-pentadlenoylaminoaniline ,

2- (ß-Pöiit adienoylaminö) äthylamino-8 -naphthoi-6 -sulfonsätire ₉

1 -Pentadienoylamino - ^ - naphthol - ^ »6'-diaulfonic acid \.

2-Pentadienoylamino-5-ilaphthol · -7 «sulfonic acido

are dyes _s oils phthalocyanine or anthraquinone dyes / which contain at least one group of formula I, in addition to the process described, can thereby be obtained

10984Π / 1663

denρ that a sulfonyl chloride, for example copper phthalocyanine sulfoncalorido is reacted with a compound which has a primary or secondary amino group in addition to a Group of Formula I contains an example of such a compound is N-pentadienoyl-p-phenylenediamino

Dyes which contain at least one group of the formula

^H 5

-GO-O «C-C a C.

1 ^H 2 ^ "4

contain, in which R ₉ R, _r R ₂ , R ^, R ₄ and Rj- have the meanings given above _p where this group is bonded to an aromatic nucleus or a -BOgNH- or -SOplI «alkyl group via a methylene bridge group, can also be obtained in addition to the processes already described, that a dye compound or a dye intermediate compound, which one or more. -SO ₂ KHg- or -SOoM-alkyl groups or contain one or more aromatic nuclei which have replaceable hydrogen of fat oma, aromatic nuclei reacted with N-methylol, N-Mathyloläther- or N-halomethyl derivatives of the corresponding unsaturated carboxamides, which replaceable hydrogen atoms are in particular benzene nuclei which are free from sulfonic acid groups or derivatives thereof and have electron-donating substituents,

109840/1663

such as hydroxyl, amino and, in particular, lower alkoxydes

are substituted
lower JÜLkylgruppeitf, particularly suitable for shipping to

Production of desired dyes are dye compounds or dye intermediates "which eLüG or more Groups, the formula

V V

-UH - ^ / "^ _{--OH 3} or -MH - ^" ^ - OH-

* £ «« r XSSSSr

The IT-methylol- and If-hologeamethylderivate of the Unsaturated carboxamides can be prepared in the usual way will. So can the N-methylolamides by reacting of formaldehyde with the unsaturated carboxamides, for example ßorbamide, under basic or weakly acidic conditions be made <,

The reaction between the N-methylolanide and the dye compound or dye intermediate is usually carried out in

known
Presence of / acidic condensation or dehydrating agents carried out _t whereby concentrated sulfuric acid is preferably used for this purpose o The reaction can be carried out at a temperature between 0 and 20 ° 0, but if desired, slightly higher temperatures can be used »

109840/1663

~ 27 -

dyes, which alndeatene a group of? oxael

«0

be included, in which R ₂ denotes hydrogen or alkyl, and R, R_ "R * and Re have the meanings given above" kttonen also prepared by "DAFL a ParbBtoffverblndung or farbstoffsswieohenyerbindung _t which one or more groups of Pora» l

contains «in which. £ has the meaning given above, with a Compound of formula

0 m CO m C

It is specified that xorin R _{2 is} hydrogen or alkyl / and R » _v Rj and the meanings given above have »Suitable compounds are acrolein or crotonaldehyde, the reaction being in a Medium such as dioxane or pyridine using eaurer or basic catalysts is carried out. The dye β or Paraffin powder products which have one or more groups

the formula

109840/1663

-H-GOCH ₂ GH

can be prepared in the usual way that! dyes or color toiTswieoJienproankte »« oak contain one or more -NHR groups »reacted with cyanoacetic acid ester or with chloroethyl chloride, followed by a treatment with an alkali metal alloy _{or similar}

Pie dyes made according to the invention are

or in a mixture valuable eum dyeing Fasermaterlalien and polymeric F1lnwn ₀

Faeermaterlalien, welohs made with the according to the invention th dyes can be colored are lertilmatertalien, Leather and skins "Xextllmaterlallen" which can be dyed on these catfish "are both natural and artificial Teztile materials, for example such »which are natural Cellulose fibers, for example cotton, flax, jute »hemp» siaal and hemin contain »regenerated cellulose fibers, for example viscous artificial silk «cd cuprammonium kunateoids, Cellulose ester fibers, for example cellulose acetate and cellulose triacetate, natural free fibers such as beieplelewelse Wool, silk and mohair, regenerated protein fibers, synthetic polyamide fibers such as nylon-66, nylon · -6 and

109840/1 663

~ 29 -

Hylon-11, modified synthetic polyamide fibers, aroitisoh »polyester fibers» for example polyethylene terephthalate, modified polyester fibers, polyaorylnitrile fibers, modified · polyaorylnitrile fibers, polyurethane fibers and polyolefin fibers, for example, polypropylene and fibers, which are made up of mixed polymers, made from other synthetic polymers of vinylidendinitrile and vinyl ethers and mixtures of the fibers mentioned. The θβ materials can be in the form of loose fibers, slivers, yarn or piece goods. ₀ Polymer © films »that can be colored with these dyes are polyester, polyamide» polyimide, polyurethane, polyvinyl and polyolefin materials

The new dyes containing one or more vaaserlÖBlichsiachan * de groups as ζ · Βο sulfonic acid groups are particularly vonZaLluloaetextilmaterialien sum dyeing such, B 'tree' wants and Polyamidtextilmaterialiezi as Z ₉ B ₀ nylon and wool, useful. The new dyes, which contain no water-softening groups, are particularly useful for dyeing polyethylene tertphthalate materials, cellulose acetate textiles including tri-acetate materials, polyolefin fibers and synthetic polyamide textile materials such as ZoB, Hylon. Of course, as is the case with known dyes, the suitability of a dye for a particular fiber depends on its general structure

109840M663

de a dye and not just from the present one or more Groups of formula I from »

The dyes of the present invention can be applied to various textiles and other substrates "whereby the dyeing, KIoU and printing methods described in the literature can be used and dyeings are obtained which have a suitable fastness to light and wet treatments" For example, the water-soluble dyes can be applied to cellulose, wool and synthetic polyamide textile materials by treating the said textile material with an aqueous solution of the dye in the presence of the usual dyeing auxiliaries at a temperature between 0 and 1 (X) ⁰ C. which do not contain any water-related groups can be applied to cellulose acetate, polyester and synthetic polyamide textile materials. by treating textile materials called cLqt with aqueous dispersions of the dyestuffs, using conventional techniques of the dyeing process are based »

109840/1663

It will jjedooh to get the maximum benefit from the improper Dyes, especially a maximum fastness to wet and / or -a, pull out, preferred that they apply to the fiber materials and the polymeric Films are applied together with a Hittel j of one Polymerization of polymerizable ethylenically unsaturated Connections induced "

Agents which are suitable for inducing polymerization of polymerizable ethylenically unsaturated compounds are generally known and are usually referred to as polymerization catalysts or polymerization initiators example, have been already proposed for the polymerization of ethylenically unsaturated compounds * Suitable agents are ZOB ₀ organic peroxy compounds, never peroxides, hydroperoxides, peracids, peresters and percarbonates such as ZOB _o acetyl peroxide, Proplonylperoxyd, benzoyl peroxide, lauroyl peroxide _f Stearoylperoxyd, t-butyl peroxide, t -Amylperoxyd, 4-GhlorbenzoylperoxyÄ, 2p4 ~ Dichlorben2oylperoxyd, Hethyläthy3.ketonperoxyd, Cyclohexanonperoxydi t-butyl hydroperoxide, C-imolhydroperoxyd, Tetralinhydroperoxyd, t-ButylperbenzoEt, di-t-butyl peracetate butyldiperphtlialatf t ~ _s Peressi gsä-xre, perbenzoic acid,

109840/1663

^BATH

Performic acid, diisopropyl peroxycyl carbonate and acetyloyclohexanesulfonyl peroxide, azo compounds such as ZoB ₀ 1,1'-azohisisobutyronltr11, 4 * 4 * -azobie-4-cyanopentanoic acid, 1,1 * -azobie-1-cyanocyclohexaydopropyl'-1-cyanocyclohexaydane, 1,1'-azohisisobutyronltr11 , 1,1'-AÄobie-2,3 ~ <methylvaleronitrile, and inorganic compounds such as ZoBo hydrogen peroxide, Airmoniumpersulfat, Kaliumpersulfat, Katrlumpersulfat, Cer-einmonliam-Nltrat and Cer-Aianonium-sulfato Other suitable free radical generating systems are Z ₀ B ₀ Redozsyeteme _c Geeignote reducing agent for use in redox systems in Verolndung with the corresponding oxidizing agents are ZOB _c Eieen salts (II), such as ₆ Bieen (H) sulfate and Si s (II) ethylenediamine -ämmonlumsulfat _t ^ tetraesBigBäure , Metallformaldehyd- and -acetaldehydsulfoxylate such "B ₀ ITatriuinformaldekydsulfoxylat, sodium sulfite, Natriumbisulf it, Natriumtaet abieulf it, sodium hydrosulfite, Hatriumthiosulfat, sodium sulfide" sodium hydrosulfide, Thioglyooleäure and their water-soluble salts, cysteine, oxalic acid, formic acid, tartaric acid, xhiocarnea, thioham- _x stoffÄoxyd, ascorbic acid, hydroxylamine, hydroxyleminnalga, such as the hydrochloride and the sulfate, hydrazine, hydrazine salts, such as ζ.Bc the hydrochloride, d-Glucoee, dextrin, glyoxal and sulfinic acids and mixtures of such agents. Suitable oxidizing agents for the use of the oxidizing part of the redox system in connection with the corresponding reducing agent are SoB ₀ hydrogen peroxide,

109840/1663

BATH

- 33 -

Ammonium persulfate, potassium persulfate, I potassium permanganate, potassium bromate, Potassium perchlorate, iron (III) "chloride, ethylene dibiguanide complex salts" from triple positive silver and the various organic peroxides and hydroxides given above were = equipment from oxidizing agents can be used, and together with the redox seeds, smaller amounts of activators for systems such as eg copper sulfates can be used Hydroquinone and silver nitrate, are used »

Other compounds can also be used, of which it is known that all initiators act for the radical polymerization of ethylenically unsaturated compounds, such as SoB ₀ diazonium compounds and stabilized diazonium salts, cobalt complexes such as ZoB, dichloroaquotriaianinobalt chlorid and trinitrotriamminocobalt, such as ZoB ₀ benzene and p-toluenesulfinic acid, a transition metal _{carbonyl, such as a e} B _o molybdenum carbonyl, cobalt carbonyl and nickel carbonyl, possibly in conjunction with a phosphine, in conjunction with an organic halogen-containing compound _P such as _e B <, carbon tetra chloride , Carbon tetrabromide, chloroform, bromo-formant and N-bromo-succinic amide, N-nitrosoacylamines such as ZoB _Q N-nitrosoacetanilide, II-nitrosocarbanilide, lijli'-dimethyl-N ^ N. terephthalamide and N-chloro-p-toluenesulfonamido

109840/1663

BATH

fo'enr. desired and if appropriate; came. the use eJ
chemical Kittels be added as free-radical generating system through the use of other means of generating free radicals or replaced * For example, a! textile material, onto which a dye of the invention is to be applied, the radiation of, for example, an ultraviolet ·, x-ray or Sammastrahleniuelle or exposed to an electron beam.

In a dyeing process in which the dyes according to the invention are used, the polymerization catalyst can be added to the dyebath at any suitable stage. So it can be added at the beginning of the coloring process, but it can also be added afterwards »if a partial OU3V largely complete introduction of the dye in
the fabric or other substrate has taken place. On the other hand, the dyeing process can also be completed without the presence of a polymerization catalyst, whereupon the textile material is then converted into a solution or suspension of the catalyst in water or an organic one
Solvents can be thawed & t * If necessary, can
dia treatment; with the polymerization catalyst by removing the textile material from the solution or suspension,
which contains the polymerisation catalyst, and by subjecting the textile material to eiA? Heat treatment at the end

109840/1663

; ■■ _.-, - * BADORiGiNAU

to be brought. Torsufsvels · should be during the of the textile material bit the polymer! i ^ tlonskatalysator a Temperature in the range of 40-200 ° C reached «ground« with a “Another variant, the PolyTerisationsketalysator can work on the Textile material applied before the dyeing process «earth · Dft · most suitable method but application of the catalyst depends something rom su coloring substrate from «If natural« or synthetic polyaaid textiles dyed «earth, then ed in general, preference is given to subbing the catalyst in an aftertreatment. la case of a slot procedure can textile material with st & ts? Xiusung or dispersion, which contains the dye and the Folyaerig & tionslsxitalysator, padded, among other things then steamed. AlteraatiT can change the textile material “ooh sdLt a solution »or dispersion · which contains the oil, padded / dried (possibly by heating) and then again old of a solution or dispersion that has the lysator contains, padded and heats up or steamed "earth"

In the case of a printing process, the polymerization catalyst can be incorporated into a printing package with a suitable dye are introduced »which are applied to the textile material «Can be grounded, velohes following the action of heat or Is subjected to steam. Alternatively, you can jerk the contains a dye of the kind that can be found on a textile » material are applied, the bit a polymerisation *

109840/1663

has been impregnated with the catalyst, whereby the soleplate is protected from the action of warning or dew is »often a further variant · can be a printing paste that containing a dye according to the invention, are applied to a textile material, which is subsequently in a hot solution or suspension of the polymerization catalyst is immersed, or the printed textile material can also be old a solution or suspension of the polymerization catalyst impregnable and subsequent to the effect of warmth or To be subjected to steam.

The textile material can be printed using one of the tibliohen and known methods for applying print pastes to textile fabric, for example by roll printing, screen printing, block printing, spray printing or stencil printing ο you can also use the Ublioher printing auxiliaries such as SoB _o urea, thickeners, for example Hethylzelluloee, starch, Ifegominosenbohnengum, Hatriumalginat, water-in-oil EiaulBionen, oil-in-Wosser process emulsions, surfactants Kittel, sodium mnitrobensolmalfonat, and organic liquids, such as _e B <. Ethanol o

10984Π / 1663

BATH ORIGINAL

■. ■ - 37 r

u the most suitable amount. Polymerisationakataljmtor, for use in dyeing, blots and bediuokvtrfshxm, is usually in the range of 1 ~ 500-4 _tons based on the weight of the dye used. The most suitable amount for use in a particular case depends on various factors such as Z ₀ B ₀ on the exact nature of the catalyst, the structure of the dye, the dyeing process used and the required shade depth

If the dyes according to the invention are applied to textile materials together with a polymerization catalyst, they result in dyeings with remarkable fastness to wet treatments. On this basis, the dyes are strongly superior to the corresponding dyes which do not contain any groups of the formula X. It is assumed that this is in the formation of colored polymer onto or into the textile material has its ground ₀ in addition to improved Na8eehtheit the effect can of Polymerisationekatalysatörs be demonstrated by solvent extraction of the colored material "the resistance to solvent extraction is with materials to which the dyes together with a polymerization catalyst have been applied, much higher than with materials that have been colored without the use of such an agent »

109840/1663

The dyes according to the invention can optionally be applied to the textile materials together with one or more other compounds which contain at least one olefinic group which can be polymerized by a radical mechanism.

Examples of suitable polymerizable monomers are:-olefins _β- vinyl aromatic compounds, such as ZoB, styrene, halogenated styrenes, α-methylstyrene, vinyl toluene and divinylbenzene, β-unsaturated θ carboxylic acids, such as SoBo acrylic and methacrylic acid and other substituted acrylic acids, as well as the nitriles, amides and esters thereof, vinyl esters, vinyl ethers, vinyl ketones, vinyl chloride, vinylidene chloride, N-vinyl compounds, such as Z ₀ B ₀ vinyl carbazole and vinyl pyrrolidone, unsaturated dicarboxylic acids, such as z _ü .B _r JPumaric and kaleic acid and the esters and amides thereof and dienes ₀ Other useful compounds containing one or more polymerizable olefinically unsaturated groups © are, for example _o: Trieacryloyl-hexahydro-s-triazine, 1,4-butanediol diacrylate, H-acryloyl Urea, allyl alcohol, triallyl cyanurate and compounds derived from phenols and aromatic amines, examples of such compounds which may contain one or more water-solubilizing groups nts are AcrylaaidobenzoeBäure ^, ^ -Acrylamido-nitrobenzoic acid 6-, N-Aorylamidoanilin-5 or H-sulfoneäüre, 1 _f-J ^ Bieaorylamidobenzol- sulfpnsaure, 2-Aeryl ^ unidonaphthalin-6 · -

109840/1663

or -7-sulfonic acid, S-Aoiyliaaldonaphthalin-S, ^, ^ -3 * 6- otter «5 e 7-disulfonic acid» 2 ~ A0rylaMdo ~ 8-naph / fcaol-6-stsl £ onic acid, 2-Acrylainido-5- naph1 ^ l-7 ~ 8Ulfonic acid, 1 -Aerylamido-8-mpfctbjeu, -3 ₈ 6-disulfonic acid, 1 ^ 4'-Acrylainidop) 3. (2nyl) -5-methyl-5 * pjTnsuso- .. lon, 1- {5 ^f -Acryla ^ do ~ 2 ^l -metliyl-5'-salfophenyl) «5-methyl-5- · pyrasolone, 4 ~ acrylamidophenol υηά the substituted acrylamido» pentadienoylamino, substituted isntaalenoylamino vcaü. Vinyl sulfonyl analogs of the above phenol and alumina derivatives _and polymerizable monomers of these types are incorporated into the dye bath or into the printing paste together with the fibers and other ingredients

The dyes of the present Brfindvzig can even in the absence of substrates polymerized ver & en, where colored homopolymers are obtained _o By Mj.tverxirend "ng of copolymer isierbaren Monomören which can be colored or colorless, colored mixed polymers can be obtained _t, the dyes may be prepared using the common cathode, which are described in the literature, pol ^ iaeris5.3rt werdsn _o Examples of such methods are block, Iiösung- _S emulsion or Suspensionspolymerisationsmethodeno Dj.e usual polymerization catalysts such as Zob. those already mentioned above, or high-energy irradiation, can be used. Other conventional aids can also be used; like ZoB _o emulsifiers ^ treasure colloids, thickeners,

109840/1663

^ßA *> ORIGINAL

/ mtisehaumroittel, buffers, and chain transfer agents such as _ζ σ Β ₀ Kohlenstofi'fc3i; rachlorid _f n-butyl mercaptan -and- Dodecylmeroaptan The appropriate amount of n & Polymerißaticnekatalysatoron is use of these methods is usually in the range of 0.005-20 Gewe- S, based on that? total weight of dye used, and possibly _c comonomer used ₀ the polymerized dyes könr.en in the form of powders, granules or lumps are obtained, and they can quantities in the manufacture of Pig-P and 7onr.gegenständen the versohj.edensten type warden verwandet _o

The new polymeric colorants, which are in the form of powder and are either individually or in the form of a smell, can be used as pigments for coloring paints, where they give a wide range of color shades with good fastness, especially to solvents, if they are introduced into alkyl and melamine resins and other paint media £ "Alternatively, the colorant may be used as pigments for the coloration of synthetic polymeric materials such werdsn ,, ₀ B" polyvinyl chloride, polyethylene, polystyrene, or cellulose acetate.

By grinding the new colorants with water and a dispersant, like ZoBo dinatrium naphthylmethane-di-ß-sulfonate, the colorants can be pasted in the form of pigment. to be obtained

109840/1663

BATH ORIGINAL

ψί <. '

den, vfie sif? for the .production of JLänulsAoaißfarbenj, for the i "'ö> .irrn? g of l'apeten? for textile? ruels. = - for the coloring of' Et.pj.ot ynci Papxerlatalnrrceat, for the E: mai * beii7ung in.-Farbeni 'or lithographic varnishes or suitable for use

pg-ion τοη faaerbiidenden i'Iaterialien _s such as B.- ^ .U ^ '- rose-. exgnsii .. With the sex * iirvend aind aie because of

tlieit 'note o

B-Ja T: _t rj.ii; Vc ^ -trlrd by the following examples he closer -. '. ·.!' .. ori; Bis -La; », games are not in a restrictive sense β.τ.χζ \ ζ £ ο.: Ι && η., A'JXq 1ie ± 2, e are expressed in weight

£ o ifjpi e \ J ^ .... ■■ '

ΐ; aif: l'ö3Ui5g of 17 ¹ I eil en 4 - »- A.iain-o-» 2 ¹ 'l:; 7dros: y' -. 5 ⁱ '"iflethylasobenzol Iu olncvr iilackimg auo 480 ropes of acetone and 100 parts of water tiled stirred at ⁰ C CMO, and 17 »5 parts Fentadienoylchlorid be t-rabrend 'sugegeben min _30;, wälirenddessen the pH by tU) * <■ * ■ iiaor vräßrigen NatriOmcarbonatlösiing swischen 7" and S

gehal.ten vird.v The resulting mixture is then geriüirt at 20 C, until most of the acetone dea vex'dampft -is, the atiBgefallenG tind dye is abfl3.triert _f au dried and x ¹ * 85 Toilori 2-'λ bhoxyathanol viikristalliaierte The resulting yellow crystals of 4 ~ ~ Penΐ.attienoyl είJ3lirlO ■ '■ 2' · "hydro2: y · ^J -5 --πϊethyl ~ azobenaol ßchmelzan UNOE in 190-1-91 Q ⁰ are in aqueous .einem.

_{; :} \ 10984Π / 1663

BAD r> Dfi-M «.t«.

Medium dispensed, im. can be applied to textile materials

Instead of the 17/5 parts of ientadienoyl chloride used in the above example, 23 parts of 4-chloropentadienoyl 'eliiorid or 20 parts of sorbo.yl chloride are used, where 4 ~ {/ }.'-Ch3.oropenuadienoylamino) -2 "-Iydroxj-5 ^lf -methyla! 3Olje2i25ol with a melting point iron 174-176 ⁰ C bzv _o 4 ^ orboylaE & no-2 '~ P hydroxy-5' -methylazobenaol with a melting point of 216-218 ⁰ C obtained x ^ erdeno

The dyestuffs obtained in this way (0.02 part) can be converted from a dye bath containing water (50 parts), potassium dihydrogen phosphate (0.05 l part) and the disodium of methj ^ lendinaphthalene-sulphonic acid (O _r O75 parts) to polyethylene terephthalate textiles ( 2! parts) applied by dyeing under superatmospheric pressure wälirend 30 min 130 ⁰ bai G advertising tk the * is the fabric rinsed in cold water and

treated in a bath containing 50 parts of water and 0.1 parts of 1,1'-dicyano-1,1 ^} -aso-cyclohexane, ^{treated at 0} O for 50 minutes

The dyed fabric is rinsed in cold water, and 10 of the condensate from Honylphenol and 8 mol Ithylenoxyd in 1000 parts min at 6O ⁰ G in a solution of 2 parts tf

1 0 9 8 U ^: 0 7 1 6 6 3

BAÖ ORIGINAL

treated., The fabric is rinsed and dried, Bs is obtained a splendid yellow color, the opposite dry ■ Full coverage & aate treatments have a temporary authenticity

own"

On the other hand, the dyes can also be applied to a cellulose diacetate textile by dyeing for 1 hour at 85 ° C. from a dyebath containing water (150 parts), sodium olyl sulfate (0.3 part) and dye off (0.04 part). The fabric is rinsed in cold water and placed in a fresh bath, the water (150 parts), the disodium salt of MetliyleBdinaphthalenesulfonic acid (0.2 parts) and 2.2 * 01θ7βηο-2.2 ⁵ -βΒορΓορ8η (0 _f 2 parts) contains, ^{treated at 90 °} C. for 50 min. The Textiletcff is ir 'rinsed anion Uaaser and washed for 10 min at 50 ⁰ C in a solution of 2 parts of the condensate of nonylphenol with 8 moles of ethylene oxide in 1000 parts of water. The textile fabric is rinsed and dried to obtain a splendid yellow coloration, which has a prior authenticity _{0 in relation to wet treatments}

Eija Zellulosetriacetattextilstoff Tonn instead of Zelluloeediacetattextilstoffs (4 parts) Terwendet be, in which case the coloring at 100 ⁰ C is auögeftihrt ^ The dyed and treated Zellulosetriacetattextilstoff besitsri; a bright yellow shade with an excellent authenticity against Daaqpf-S ^ against tfaeöhen under strict conditionsc

109840/1663

Example 2

A "solution of 1.25 hone 4 ^ yano" 2 ~ ohloroanilin is in 20 parts of glacial acetic acid at a temperature below 1O ⁰ C by the addition of 3.3 parts of a 36 ^ aqueous hydrochloric acid followed by addition of 0.6 ropes sodium nitrate; in 5 parts of water dlazotlerto the diazo solution obtained in this way is added over 10 min to a stirred solution of 2.2 parts of methyl-N (β «-N * methyl-N ¹ -sorboylaininoethyl) aniline in a mixture of 60 parts of water and 6 parts of a 36% strength aqueous hydrochloric acid at 5 ⁰ G were added. After stirring for 1 st, the pH of the mixture is increased by adding an aqueous Natriumaoetatlösung to 5, and after a further 12 et continuous stirring, the pH is increased by addition of an aqueous Natriutnfcydroxydlßsung further to 8 ,, The product is filtered off and washed with water The N-Ethyl-Ä- (ß-H'-methyl-N ⁵ -sorboylaminoethyl) aniline used in the above example is obtained by acylation of the K-ethyl «Ii- (ß-Bi ^{: i} --li © thylaiQiii.oäthyl) - imfil "" obtained with sorbyl chloride in aqueous acetone solution at pH 7 to 8 *

The dye described in the above example can also be obtained by adding Sorboylohlorid to a solution of 4TfN-lfchyl-N- (β-H * -iMthylaiBinoäthyl) 7fü »ino-2 ^l -45hloro ~ 4 ^l -cyanoassobenzene in aqueous * acetone at pH 7 to be received by the 8th «

109840/1663

Used instead OCE in the above Example 2.2 parts ff-ethyl H (BN "-metl ^ l-N'-sorTjoylöJninoathyl) aniline to 2, 1 Part

& -Ethyl «« N (ß-li '-methyMi' «pentadienoylaininoethyl) aniline, applied, the dye ^ pSF-C

Έ ^! ~ pentadienoylaminoethyl) / ainino-2'-chloro-4'-cyanoazobenzene

obtain

The pentadienoylamino or sorboylaniino dyes obtained by the above “method can be applied to polyester textile fabrics according to the method of Example 1.” A scarlet coloration is obtained, which has a preliminary fastness to extraction with pyridine, to trootoenic hot overdyeing and to vigorous washing ₀

The pentadienoylamino or amino dyes obtained in this way can also be applied from a dye bath to lofted nylon 66 ~ textile known in the trade as "Banlon" (4 parts), the water (150 "parts") oleyl sodium sulfate (0.5 part) and the dye (0.04 part) contains ο The dyeing is carried out at 100 ° 0 for 30 min, • whereupon the dyeing bath contains potassium sulphate (O ₁₅ I part) and natriurabisul · · ■ fit (0 _e 05 Parts) are given ₀ The dyebath is held at 100 ° C for a further 30 minutes, the textile is then removed and 10 minutes at 60 C in a solution of 2 parts of the condensate of nonylphenol in 8 mol of ethylene oxide in 1000 parts of V / aseer

1 09 8-4 0/16 63

- · 45 - washed, The fabric is rinsed and dried

A scarlet color with excellent fastness to sweating and tight meshes is obtained.

Example 3

A solution of 3 »ropes 64 4-Amino ~ 2,5 ~ dichloro ~ ben20lBUlfoh-U- (ß-pentadienoylaminoäthyl) in 20 ainid ropes glacial acetic acid is duroh at a temperature below 5 ⁰ G addition of 3.5 parts of

aqueous hydrochloric acid and subsequent addition of a solution of clay 0.7 parts of sodium nitrite in 5 parts of water diazotized The diazole solution obtained in this way is during 15 min to a stirred solution of 1.95 parts of H, ii-di (2-hydroxyethyl-m-toluidine in a mixture of 50 parts of water

36% t.gei » _o

and 2.5 parts of aqueous hydrochloric acid of 5 ι C ,, added eineir After 15 min of stirring, the pH is increased the ßemißchs duroh adding an aqueous ITatriumacetatlöeung to 5 and is st after a further stirring for 2 aas product filtered off and _f with water, the contains some sodium carbonate, washed _o

The 4 "amino-2 _f 5-dichlorobenzenesulfon ~ N ~ (ß-pentaaienoylaminoethyl) amide ^{used in the above example has a melting point of 109 0} C and is obtained by acylation of 4-amino * -2 _f 5 - ^. I <- · Cblorben2olBulfon-N- (ß-Amiiaoäthyl) amid with Pentadienoylohlorid in aqueous acetone solution at pH 7 to 8 obtained>

10984Π / 1663

., 47 -

Instead of the 3 (Ainino-2 _f 5 ~ 64 parts 3IC 4 ^: blorobenzolsulfon-N- (P ~ pentadienoylaminoäthyl) amide, the Xm above example were used, 3 ", 78 parts of 4-amino-2/3-dichlorol) en2oXeulfon «-N- · (ß ~ 8orboylaminoäthyl) ainid can be used, which is prepared in an analogous manner«,

The pentadienoylamino- or sorboyl "obtained in this way" Amino dyes can be obtained by the method of Example 2 a built nylon 66 fabric: * f can be applied «it a red coloration is obtained which has very good fastness to perspiration and washing ο

The pentadienoyl or sorboyl dyes produced in this way were obtained can also be described in Example 1 by da3 Process applied to cellulose diacetate fabrics * 33s a yellowish-red color is obtained, which is very fast to steam ironing and washing »

Example 4

Bine solution of 4 parts of 1 -MetbylaininQ-4 ~ (4 '-aminoanilino) anthraquinone in a mixture of' OQO parts of acetone tffld 200 parts of water nird stirred at 0-10 ⁰ C, and 5.5 parts Pentadienoylchlorid added during 15 ain During this time the pH is kept between 7 and 8 by adding an aqueous sodium carbonate solution. After the acetone has evaporated

109840/1663

BADORfGlNAL

~ 48 the product is filtered off and washed with water

Instead of the 5t5 ropes, pentadienoyl chloride. which were used in the above example, 4.6 parts of Sorboylohlorid are used »whereby 1-methylamino * 4- (4 ^l ~ sorboylamirioanilino) - · anthraohinone is obtained * instead of the 4 parts of 1-Hethylamina 4» (4 ^f -aminoanilino) anthraquinone _f which were used in the above example, 4.35 parts of 1- (2'-hydroxyethyl) amino-4 '- (4'-aminoanilino) anthraohinone are used, 1- (2'-hydro3tyethyl) amino4 ~ (4' - pentadienoylaniinoanillno) anthraobinon get?:, willo

1 ~ Methylamino4 «- (4'-pentadienoylaainoanilino) anthraquinone (0.02 ropes) can be applied to a polyester textile (2 ropes) in a förbath that contains water (50 ropes), oleyl sodium sulfate (0.025 ropes), potassium dihydrogen phosphate (0.023 ropes) and the Dinatrtttmsalz of Methylendinaphthalin "sulfonBäure contains (0 _f 05 ropes) * the color is carried out for 50 min at 130 ⁰ C. The Sextiletoff is treated in cold water ge ~ rewinds and then 30 min at 110 ⁰ C in a bath "the water (50 ropes), 2,2'-dicyano-2,2'-aaopropan (0.1 rope), o ~ £ Dichloroben ol (0.2 ropes) and Oleylnatriumeulfat (containing 0.05 ropes "the Sextilstoff is gftepült and iO min at 60 ^w C in a solution of 2 ropes of condensates AUB nonylphenol having 9 ethylene oxide Hol, dissolved in 1000 ropes water , washed"

109840/1663

ßAD ORIGINAL

The fabric is rinsed and dried «. Br is dyed in a golden blue shade with very good fastness to dry hot over-dyeing and harsh washing .

1 «(2 ^l ~ Hydro2QTäthyl5amino-4- (4- * ~ pentadienoylaininoanilino) -anthraquinone can be applied to Hylon by the method of Example 2 _o A greenish-blue color with excellent fastness to sweating and washing is obtained«

Example ft

A solution of 3 * 8 parts of the sodium salt of 4-Eydro3 ^ y-5- (4 * -aminophenylazo) -ß-aininonaphthalene ^ -sulphonic acid in a mixture of 200 parts of acetone and 50 parts of water is at 0-1O ί is kept stirred at ⁰ C, and a 7 _t ropes Pentadienoylchlorid be added during 10 min, the pH during the Zugs.be by a '■ _r aqueous solution of sodium carbonate-7-8 "After most of the left exhaust steam Acet ons s j is _g the product is filtered off and dried,

Ϊ "■ '' ■ '' '

• Instead of the 4.7 parts Pentadienoylchlorid that in the above Bel · -. ■■■ were used game) 'are 5 * 2 parts sorboyl chloride · ν · η · Λν DETP thereby obtaining a similar dye.

1098 40/1663

«Ftino The PentadienoyOi · or Sorboylealno obtained in this way Dye can be applied to nylon 6 textile (commercially available as ¹ HJeIOn ¹ *, Courtalda Ltd ·) «The parbetoff (0.04 parts) is dissolved in water (150 ropes) Susanne Bit Aseonium acetate (0.12 ropes) «The Hylon-6 textile fabric (4 parts} is then treated in this» dye bath for 20 minutes, and the dye bath is exhausted from formic acid (0.04 part),

Potassium persulfate (0.1 part) and Hatriumblsulflt (0.1 rope) are then set to the dyeing which is ^{kept at 100 0 for} another 30 bin. The dyed textile is rinsed and 10 min in a solution of 2 ropes of the condensate nonylphenol washed with 8 moles of ethylene oxide at 60 ⁰ O and dried ο boron fabric is dyed in a red color magnificently "which has a very good Bohtneit against sweating and hot washing ₀

When the 4 ropes of Nylon-6-Textilatoff go through 4 ropes of a Serge sextile made of merino wool (botanv wool «ere · fabric) «then a red jacket will sit one obtained very good fastness to sweating and washing »

Example 6 A solution of 4.31 ropes of the Hatriumsalaee τοη i-Aaino-4-

10984Π / 1663

(3'-Andjioanilino) antiiraoiiinon-2-eulfon8äare in a kit of 200 parts of aoetone and 75 ropes of water is ^{stirred at 0-10 0} C, and 4 (7 parts of pantadienoyl chloride "earth" added over 10 min, meanwhile the pH by adding a Odd solution of sodium carbonate between 7 and 8 is kept, "Lake acetone is allowed to evaporate, and the i-Aialnc- ^ i ^ '- pentadienoylaminoejdJ.ino) anthraquinone" -2 "-sulfonic acid is filtered off and dried

Instead of the 4.31 parts of the sodium salt of 1-Amino-4- (3'-aminoanilino) anthraohinone-2-sulfonic acid, which was used in the above example, 4-73 parts of the sodium salt of 1-Amino-4 ~ ( 3 '- amino ^ S' »4 '» 6' —trims thylanillzio) anthTÄOhinon— 2-eulfonic acid used, whereby a similar dye is obtained. »

Sin each of the pentad produced in this way! EnoylaadUaofarbstoffe can be applied to nylon 6 Textiletoffe by the method described in Example 5 "Bs impeccable blue color is obtained which has very good fastness to" excess sweating and Väschen _o

Example 7 A solution of 4 parts of the "Färbet off β, whose Foreel hennlhemd."

} ₁ ^ (Po «phthalocyanine)

109840 / T663

speaks, in a mixture of 100 ropes. Of water and 100 parts of acetone is stirred at 0-1O ⁰ O, and 2.8 parts Pentadienoylohlorid be sugegeben nin during 10, the pH during the 8uga.be by an aqueous solution of sodium carbonate is kept sniff at 7 and 8 "that acetone is then Allowed to evaporate and the product, which is essentially

OuPC (SO ₅ Ha) ₂ ^ ₅ <S0 ₂ NliCH _? CH ₂ miCOCK «CH.CIIsCI! ₂ V. -let, is filtered off and dried ο

The dye (0.2 parts) can be applied to a bleached "Indian Head" cotton fabric from a dab bath »welohee also sodium carbonate (water-free) (0.04 part), urea (4 parts), di-tert-butyldiperphthalate (0.025 parts) and Vasser (20 parts) containing the KLoteen · Haoh is the textile "material dta warm air dried and then 20 min at 110 ⁰ C gedftjqpft. The fabric is then 10 parts of sodium carbonate 2 min (anhydrous) at 100 ⁰ C in a solution of clay and 3 parts Seifenflooken (per 1000 parts) and then rinsed and dried ·

The fabric is a deep turquoise color an excellent smoothness towards Bohwitsen and spicy ones Colored vials.

109840/1663

Example 8

O9 04 Parts of the dye3 l-AjDino- ^ i ^^ pentadlenoylamiiiOoulfonylanilirLo) anthrachine-2 ~ ßulfonic acid in the form of sodium bgIzqb are dissolved in 150 liters of water and 4 tall of a twisted nylon 66 fabric dyebath "introduced After heating the dye bath to 100 ⁰ C 0.04 ropes acetic acid are added, and dyeing is 30 min at ⁰ C continued 1OQ ^ M of

0.1 parts of ammonium persulfate and 0.1 ϊθϋ HatriuoKetabisulfit. made ,, and as "dye bath is another 30 minutes held at 10O ⁰ C. The Terfcilstoff is removed and washed." B ' _{M will have} a bright blue coloring with an excellent Waaoheoht * U-, _{meaning &} ■, ~ ■. ': ■ ..- .- ■■■■; -.-, -.- .-. ■., - .. ■

The dye of the above example is obtained as follows! A solution of 2.5 ropes of the sodium alumina of 1-amino * 4 '- (3 * -sulfaraylanilinoJanthraquinone-E-sulfohic acid in 75 parts of water and 200 parts of acetone is ^{stirred at 0-10 0} O, and 7.4 parts Pentadienöylohlacid be jnirtzugegeben for 30 ': _and the pH wänrenddessen by simultaneous addition of an aqueous sodium hydroxide 9-10 is held After stirring eh of the G-eintöcfets during one more hour · duroh Zugabß of Bssligsäure 7 .eingestellt, and.. : Most of the acetone has evaporated, “the product is ^{1 trated and dried}

: 1 0 9 8.40 /16.63

ORIGINAL INSPECTED

Example 9

the ■■■ "■ ■

Instead of the 2.5 parts% atrium salt Qs of i-

anilijio) anthrachino2i-2-sulfonic acid _a la Sebeispiel 8 user, 2.5 ropes of the soda salt of I-Aaiiiio- ^ C? ¹ -

i-2 '~ 3ulfonic acid used. A blue dye with similar properties is obtained, "■ ....; ... ■.: -. -.._- ... . - ■ - ■

Example IO .. -., _; . - .....

A solution of OjS ieilen 4-Pentadienoylaiai23io-2'-hydroxy-5 "-methylazoben25ol ^ (prepared as in Example t) in 18.5 parts of luodistilled diethylene glycol dimethylethylene is stirred during 1 st at 130 ⁰ C exhitst-.usd 2 st The polymer is then kept t50 ° G, the polymerisation is followed diireh Chrcaaatographie and shows a nearly complete Uimrandlttng ■? μ Polymer _a The polymer is then with the addition of 75 ropes of petroleum ether (60-80) isolated. The resulting brown product is treated with ethanol -, Bandelt, and 0 _c 3 parts of a yellowish brown solid are obtained Dae * "product is, after a suitable Behänd-, _r as a:, B" sinöia IjöäUftgsiait-tel-.KiigeliBahlen for which Si Imstötoffe like. e.g. polyethylene, suitable · ,,

Example ti, '-' - ·. ■ ,, -..-. : τ: ■ -; ■ -. : -

A similar solution as in example 10, but which one is 0 _? 05 parts fif, ^, '- contains asobisisobutyronitrile, is 18 st to 80 ° C

109840/1663
- v ^*; BADORiGtNAL..

~ 55 - ■

heated, and the polymerization is caused by chroaatoeraphite tracked",

The conversion into polymer is approximate!

Next · 0.05 parts of the initiator werdsn added and the solution is heated to 85 ⁰ O 24 8t, eating whereupon the conversion to polymer is substantially eu end. The polymer is isolated as in Example 10 and ee becomes 0.1 part of yellow dye

receive © »·

Example 12

Bine reading of 0.2 ropes methylasobenssol in 8.9 parts unäest! Liierten Methylaethaorylat deviates 0.05 parts <(A'-containing Asobisleobutyrcnitril is erhitet 1CU15 minutes at 90-95 ⁰ O 50 · Ghlorofono part are the viscous Gemiach stated "do the Mieohpolyaer on sulOeen, and the product is by pouring: 250 parts of methanol precipitated · After filtration · after the vials and drying, 7 * 6 parts of yellow copolymer are obtained" The absence of a "natural dye β is confirmed by (t) bit fraction of methanol (no yellow dye is extracted) and by (2) chromatography

109840/1663

Example 13

Am mixture of 240 parts of distilled water and 120 parts umdestilliertem dioxane is introduced into a flask, as · 1st old equipped a stirrer, a thermometer, a Sticketoffelnleitung and a reflux condenser, Bin slower 8tickstoffstron the stirred solution at 20 ⁰ O 50 is duroh adn long hlnlurohgeleltet be preceded sugegeben 18 parts of the prepared in example 5 th Pentadienoylfarbstoffs "the mixture is then further stirred for 15 min at 20 ⁰ C, during which time a slow stream stickst off duroh the mixture is passed" to the mixture is then 0.09 parts Asnoniumpersulfat and 0.09 part of Hatriunmetabisulflt sugar added, and the temperature of the mixture is ^{increased to 70 0} C over 50 min. Stirring at 70 ⁰ C is continued et 1, and ee are further 0.09 part · Ammoniumpereulf at sugegebsn and 0.09 parts Hatrluametabisulfit, and the mixture is stirred for a further «hour at 70 ⁰ C, followed by further 0.09 parts of Ammouiumpersulfat and 0.09 parts Vatnummetablsulflt be sugegeben "Naoh a 17 st continuous stirring at 70 ⁰ C (Stiokstoff is slowly duroh hiadurchgeleitet the solution during the entire Brnitaungsperlode) is allowed to cool the solution at 20 ⁰ C," the polymeric dye is duroh pouring the Reactions are filed in 1200 parts of acetone, filtered off and then dissolved in a mixture of 180 parts of water and 90 parts of Dloxsn. and precipitation by pouring the solution into 1200 parts of Aoeton

109840/1663

BATH ORIGINAL

~ 57 -.

cleaned ο After filtering off, 11.9 parts of dye are obtained as a red powder *

Example ^ el j 4

Instead of the 17 "5 parts Pentadienoylohlorid that were used in Example 1, 29 cables 5-Phenylpentadienoylohlorid be used, 4- (5'-Hienylpentadienoylaiaino) - 2 · ⁿ -hydroxy - 5 ^n" fi "thyla2Obenzol having a melting point of 224 ° 0 (Zereetanxng) "If it is applied to a polyethylene terephthalate fabric by the method described in Example 1, then a splendid yellow dye is obtained, which is good fastness to solvent extraction and to dry, hot-dyeing dye becitst «

Example 15

2.83 ropes of copper phthalooyanine are according to Example 1 of British Patent 948 256 into the polysulfuride "You fast obtained in this way will be in 150

water Share / suspended at a temperature below 5 C, and the The pH of the Oemisohs is adjusted to 7 by adding an aqueous Satriuacarbonatlöaung <, Sine solution of 4 _{tons of} O2 ropes 3 ~ entadienoylajainoanilin * -6-8UlfonsS.ure (prepared as in Example 43) in 75 parts water, which 0.2 part hydroquinone contains, is added below 10 ^° C. «The pH of the mixture is adjusted for 1 hour with an aqueous sodium carbonate solution

109840/1663

kept at 7-8 »before adding 2.1 parts of Natrlisahydrogenomrbooa-fc herds and the mixture. 16 et is stirred at roughness temperature * 5 ropes of pyridine earth are added, the solution is Stirred for a further 2 hours, and the pH is adjusted with an aqueous Sulfuric acid adjusted to 1.5 below 10 ° C. 10 ropes of sodium chloride are added »to precipitate the dye, which is filtered off, washed acid-free with 10% sodium chloride solution against Congo red paper and dried at 40 ° C ο a dye is obtained »its formula approximates

(PosPhthalooyanin) corresponds to "

Following the procedure of Example 7, the dye is applied to a unmeroerized cotton filament applied. It will be a coloring with a splendid door & lsen hue, the one has good wash fastness »

Example t6

A solution of 5 $ 3 parts of the sodium salt of i-amino-4- (3 * -ß-aminopropylsulfaD ^ lanilino) anthraquinone-2 - sulphonic acid in a mixture of 150 parts acetone and 150 parts water

109840/1663

BATH ORIGINAL

is stirred at 0-5 ⁰ G, and 11.7! rush Pentadienoylchlorid be added during 40 min, the pH during which by the simultaneous addition of an aqueous Fatriumbydroxydlßsung between 9 »5 and 10.5 is maintained" will et After 1 8.4 ropes Sodium bicarbonate is added, the acetone is allowed to evaporate, and the dye, 1-amino-4- (3 ^l -β- ^> pentadienoylaminopropyl-sulfamylanilino) anthracninone-2-sulfonic acid, which is obtained by neutralizing the solution with acetic acid, is filtered off and dried "

Ans part © of the 11.7 parts of pentadienoyl chloride in the above example 13.1 parts of sorboyl chloride are used, a similar dye is obtained.,

The sodium salt of 1-amino-4- (3 '-β-ao & nopropylsulfamylanilino) -anthraquinone-2-sulfonic acid, which was used in the above example, is obtained by reacting 1-amino-4- (3 ^l -ehlorosulfonylanilino) anthraquinone-2 -Bulfonic acid with 1 ^ -propylenediamine in the manner described in British Patent 1,027,261

The dyes obtained in this way are on a

All-serge fabric by illuminating that described in Example 5 drive angry It will be a reddish blue in any case

Obtained dyeing which had good fastness to fading

109840/1663

Example 17

3.73 parts of 1 ~ (2 '-HydroxyäthyX) äinlao ~ 4 ~ (4 * -aminoanilino) anthraquinone become 40 parts of a 5 $ igei ^{at 0-5 0 O for 30 min.} Oleums are added * The mixture is ^{stirred at 0-10 0} C for 20 hours and is then poured into bis water. The precipitate is filtered off, washed with 10% aqueous sodium chloride solution until a sample shows more reaction to Congo red ke.lrte savre, and again in one Mixture of 250 parts of acetone, 50 parts of water and 10 parts of 2ri sodium carbonate solution of 5-10 ⁰ C dissolved 4 »7 parts of pentadiecioyl chloride are added over 10 min, during which the pH is kept between 7 and Θ by adding an aqueous sodium carbonate solution Acetone is the product, 't- (2 ^s "SulfatoäthyI) ■ amino-4- (4 ~ pentadienoylamiaoänilino) anthraquinone, _c abfiltrie.vfe mj.t dilute aqueous Natriumchloridlösuiig washed and dried

Instead of the 4.7 parts of pentadienoylechloride used in the above example, 5 * 3 parts of sorboyl chloride are used, whereby 1 - (2 '-Sulfatoethyl) amino-4- (4'-sorboylaininoaniiino I * anthraquinone is obtained instead of the 3 * 73 parts of 1- (2'-Hydro ^ äthyl) aioino-4- (4 ¹ -aiidhoanili33o) anthrachijion _s which were used in the above example _? 3 ^ 73 parts of t- (2 "-Hydro ^ jrathyl) amino-4- (3 'naiulioanilir ö) anthraquinone used ,

1098A0 / 1663

...- ,, ·· .. · ■, -C BADORlGtNAL

~ 61 -

whereby 1- (2 ^ä »Su3.fatoäthyl) amino-4- (3 ^ pentadienpylaminoanilino) anthraohinone is obtained

The dyes obtained in this way are applied to an interlaced nylon 6 textile fabric (trade mark "Celan") by the method described in Example 5. Each dyeing gives a blue shade which has excellent fastness to solvent extraction ₉ washing and Sweating has _o

Example t8 .

A solution of 5 »ropes 33 of the disodium salt of 1-Aminö ~ 4- (3 '-arainoanilino) anthraquinone-2,4 ^J -disulf onsäuie in a mixture of 225 parts of acetone and 15 ropes water is gerührtj at ⁰ C 5-1G and 9 * 4 parts of pentadienoyl _{chloride are added over the course of 15 minutes a} while the pH is maintained between 7 and 8 by the simultaneous addition of 2ώ hatriuracarbonate solution o The acetone is allowed to evaporate and the product is precipitated by adding 10 parts of sodium chloride, filtered off, with ί Geiger washed aqueous sodium chloride solution and

Instead of the 5 "33 parts of the disodium salt of i-amino-4"(3'-andnoanilino) anthracmnone - 2 _i 4 ^1J -clisulfonsä.i2re _!> Which were used in the above example, 5 "33 parts of the

10 9 8 4 0/1663

BATH

.62 -

Uinatriumsolsee from 1 - *** 1 τμ> —4— (4 * "tWiTiraT ^ A ft ^ anth Tm ^ iyf ^ - 2,3'-disulfonic acid used, whereby the disodium ali from 1 —Amino — 4— (4 * - p ^nt ii? ft ^ ^^ wnoyi fniw ΙποκπΙ \ l tw) ^ftT \ th ! ^p ft ^< ! * ll ⁱ 1 π o n — 2 ■ 3 * ■ · disulfoneSnre is o

You can buy dyes made in this way by the The method described in Example 7 can be applied to bleached cotton, dyeings with a blue hue are obtained which have very good washability.

Example 19

A solution of 2.62 ropes of the sinodium salt of 1-Aaino-2 — broiao- ^> 4— (4 * —inethy1.aniil'no fl ^r> 1? 1. ' N <?) ^ TiithTf * fl ^rt ?' H ^y) o ^iy > - ^ · -sulphonic acid In a mixture of 150 ropes of acetone and 150 ropes of water is ^{stirred at 5-10 0} O, and 14.2 ropes of solvent solution, which contains 2.3 ropes of pentadiolyl chloride, are for 15 min, during which the pH is maintained between 7 and 8 by adding an aqueous dilute sodium carbonate solution. The acetone is allowed to evaporate and the dye, 1-amino-2-bro »o-4- (4 * -pentadienoylmethylnwi υοηηΐ 1 1 no) anthreohinon-a'-eulfonic acid, is filed out by adding 10 ropes of Hatriueohlörid, filtered off , washed with 5 # aqueous ammonia solution and dried,

109840/1663

Dae Hatriuosals · * "» *

anthraohlnon-a'-sulfonetore that ia above example

the following process can be used:

Am mixture of 19 »0 parts of 1-amino-2,4HiibroBK) ftnthraohinon _# 24.6 ropes 4-amino-N- ^ _r tbylaoetanilld 10.0 ropes anhydrous potassium acetate, 1 ₉ 0 rope Copper (I) chloride and 70 0 ropes XthylenglyooliQonoathyläther is et to reflux for 5 stirred at 115-120 ⁰ C. The solution is filtered off, diluted with methanol and left to stand for several hours. The precipitated substance is filtered off, washed with hot methanol and converted into ethylene glycol monoethyl ether.

12 ropes of the 1-amino-2-bromo-4- (4 ^l -

warden during \ V2

at 20-29 ⁰ O eu 42 ropes sulfuric acid monohydrate even given *

The 3JSsUOg is tdnejrührt 50, and 42 parts of a 20 £ oleum for 50 enter sün left "währenddeeeen the temperature between 20 and 25 ⁰ C O is kept. Then the solution is poured into slurry, and the precipitated substance is filtered off, washed free of acid with an aqueous catholic chloride solution and dried.

Bine solution toil 15 ropes of the obtained in this way i-Amino-2-Droiao-4-K 4 * ^ J-Qoetyl- ^ fHnethylflmJnnRni T1 nn) anthra ~

109B40 / 1663

BATH ORIGINAL

r 64 -

Quinone-2 ¹ -sulphonic acid in 300 parts of water is refluxed, and 300 parts of an aqueous solution containing 63 parts of naphthalene-1-sulphonic acid and 28 parts of sulfuric acid are added * The reaction mixture is heated to the boil and refluxed for 5 hours held and allowed to cool overnight at 20 ⁰ C transmitted the precipitated material is filtered off, washed with water until the washing liquid Celts against Congo red show a neutral reaction ", and in 1200 parts of water suspended the pH is raised by adding sodium carbonate to 7.5, and the mixture is heated to 80 ⁰ C heated 60 parts NatriumchlodLd are added, and the precipitated material is filtered off, washed with dilute aqueous sodium chloride solution and dried to give the sodium salt of 1 -AmiJio-2-bromo-4- (4 '-methylaminoanllino) anthraohinon -2 · sulfonic acid is obtained o

Instead of the 2.62 parts of the sodium salt of 1-amino-2-bromo-4- (4 ^l -methylaminoanilino) anthraquinone-2 ^l -siu.fon8äure used in the above example, 2.3 parts of the sodium salt are used of 1-AiDdjio-2-methyi-4 "(4 ^l HmethylaminoaniiLlno) anthraquinone-2-sulfonic acid used, which gives a similar dye",

Any of the dyes made on these catfish can be applied to a woolen fabric, however.

109840/1663

... .... BAD ORIGINAL

5 wool ropes are moved in a dye bath "the dye 0.05" 150 parts of water and 0 ^"K 2 ¹ see containing ammonium acetate The dyeing bath is 30 min at ⁰ C 1QO held, and the dye is by the addition of Q ₉ * 2 parts Acetic acid exhausted »

1 part of a 20 # by weight (volume) Wasserstöffperoxyds and 0.04 parts of thiourea are then added and the treatment is continued min at 100 ⁰ C during 30 * The Sextil-. The fabric is then removed »rinsed in hot water and dried ο Br is dyed in a splendid reddish-blue shade, which has good fastness to solvent extraction U ¹ Id washing *

Example 20 '

A solution of 4 »9 parts of the sodium salt of i-amino-4- (3 '<~ oleomethyl-2 * -4% 6' * trimethylanilino) anthraquinonesulfonic acid in a mixture of 200 parts of Acetaa and 200 parts of water is at 0-5 stirred at ⁰ C, and a solution of 4.6 parts Pentadienoylcblorid in? 5 parts toluene is added over 10 min, the pH during which by adding a 2n 'sodium carbonate 7-8 is kept "the acetone is allowed to evaporate _P Uncl the dye _g 1-Amino-4 ^ (3 ⁸ -pentadienoylaminomethyl-2 ", 4 '"6'-trimethylanilinoj-anthraquinone-2-sulfonic acid ₉ is obtained by adding 15 parts of sodium

109840/166 3

Chloride precipitated »filtered off and dried

The sodium salt of the iJ
methylaiillino) anthraquinone-2-sulfo.i: .aiä.ure _f used in the above example can be prepared by the following procedure;

A solution of 20 parts 1-amino-4- (2 *, 4 ', ß'-trimethylanillno)' anthraquinone-2-sulfonic acid in 150 parts of a 96 # Lgen sulfur särve is stirred at 0-5 ° C, and 18.7 parts of N-HydroapyTnetbylphthalimid are added over a period of 10 minutes ο The solution becomes

ft -

18 st at 20-25 C and stirred tu cast Eiswaöser The precipitated material is filtered off, washed with water and suspended in 1000 _o iDeüen water The pH is adjusted with sodium carbonate to 7.0-7.5 and the product is filtered off and dried

A mixture of 20 ropes of the ETatrium salt of 1-amino-4 ~ (2 '.. 4 ·, 6 · -trimethyl-3 · -phthalimidomethylanilino) anthraquinone-2-sulfonic acid obtained in this way and 300 parts Ethanol is stirred at the boil under reflux, and 6 ₉ 6 parts of hydrazine hydrate are added *.

The heating mixture is refluxed for 18 st, and the precipitated product is filtered off and ia 250 parts

1 098AO / 1663

2n HatrtUBioarbonatlösuög dissolved at 80-90 ⁰ C The filtered solution is ^{cooled to below 20 0} G, and the white precipitated substance is filtered off. The filtrates are adjusted to pH 6 with hydrochloric acid, and the product is filtered off and dried, the sodium salt of 1-ΑΜηο-4- (3 '- «Βΐ1ηο- · fflethyl-2 ¹ , 4', 6 ^l -trimethylanilino) anthraquinone «2-.sulfonic acid is obtained *

attf the dye obtained in this way is applied to a woolen fabric by the procedure described in Example 19 applied «Ba a reddish blue coloration is obtained, which has good fastness to washing

Example 21

A Löeung van 9.0 parts of 1-AmiH0 '^ (2 ⁴ 4 _f ^l _r ^l -triß6tiiylanilino 6) anthraquinone - 2-sulfonic acid in 90 parts of a 96 ^ strength Sohwefeleäure irird stirred at 0-5 ⁰ C, TMAE 4 _S 2 parts IT fiydro3cyfflßthylaorbainid "ground for 10 ro j η added The solution is et at 20-25 ⁰ G for 18 and gegoesen in Biswasser» The precipitated material is abfil'öriert ■, washed with water and suspended in 400 ropes water * The pH is adjusted to between 7 ° 0 and 7.5 by adding sodium carbonate, 20 ropes of sodium chloride are added and the product is filtered off and dried, the sodium sala

108840/1663

the 1-amino-4 (2 ', 4' »6 '-trlme feb.yl.-5' -sorbamidomethylanilino) anthraquinone-2-sulfone batire is obtained. It is applied to a woolen textile fabric using the method of Example 19 6 This gives a reddish-blue coloration with good veal fastness «

Example 22

7% of the disodium salt of 1-andno ~ 4 "- ^ ¹ - (. 4 ^M " amiuo-beneol8ulphonyl) -4 '-methylaminoanllino] anthraquinone-2.2 ^l -dieulphonic acid are combined with 9-4 parts of pentadienoyl chloride by means of the in Example 18 implemented the method described, wherein 1 -Ajnino-4 · * j [4 ^v - (4 "-pentadienoylandnobenzenesulfonyl) -4 '-methylaMinoanilinoJanthraehinon *> 2 _v 2 ⁽ ' -d.Lsulfon3äixre is obtained π

The used in the above example Färbst of f base, by ^d: - £ following procedures are established:

Bin * solution of 33.0 parts of Dlnatriv.Disa3.zea of 1-amino-4- (4'-methylaminoanilino) anthrach1non-2, Z 'disulfonic acid and 9.0 parts of sodium acetate in 500 parts of water at 30 ⁰ C stirred 0.5 parts eulfatiertes Hethyloleat and 18.0 parts of 4-Aoetylaminoben8oleulfonylchlor. * li are added and daa CMnieeh is stirred overnight at 3O ⁰ C and dried "the filtrates are salted out, and the precipitated Stofie are filtered off and again ta £ 00 Share water under

109840/1663

Dares to be "β reflux dissolved 500 parts * Z * * Bwladtopp · enter and the mixture is boiled under 10 et Bilokfluß, where it is cooled to 20-25 ⁰ C, the vtrd Jällung filtered off, washed well with 2 ^1" and hydrochloric acid in WITD 500 parts of water muff gelust, preceded the pH by adding to "atrlunwarbonatlby solution Bwißchen 7 and 8 set ₀ the 25wieohenprodukt is salted out, filtered and dried" the dye can be applied by the method described in example 3 to a Wolleteitilstoff · Bs is θΙδθ obtained blue coloring, which has good vaso-fastness

Example 23

6.5 ropes of the disodium salt of 1-aaino-4-f3 ^l - (3 "-aiainob« neoyl-

»4" —dlsulfonsBwre are marked with 9 »4

Ropes pentadienoylochloride reacted by the method described in Example 18, wherein 1-amino-4 - ['5 ^l - (3 "-pentadieno-.

is obtained «.

The dye base used in the above example can be obtained by the following procedure can be prepared

A solution of 21.0 ropes of the Dinatriuasaxses of i-Aadno-4- (3 '- ^ aiinoanilino) anthraohinon-2,4 ^t -dioulfonaäure in one. Mixture of 300 parts of water and 300 parts of acetone is used at

109840/1663

Stirred 5-1O ⁰ O, and a solution of 15% ropes of 3- * ltroben * oyl chloride in 75 parts of acetone is added, while the pH is kept at 7-8 by adding a dilute aqueous carbonate solution at the same time Allowed to evaporate over Haoht, and the precipitated substance is filtered off, washed with a 5% aqueous solution of sodium chloride and dried.

A solution of 20.5 ropes of Dinatriunsalaes of 1-Amlno-4 "i 3 * - (3" -nitrobenzoylamino) anilinojanthraohinon ~ 2,4'-disulfonic acid, was obtained did in this manner in 600 ropes water of 60 ⁰ C is made alkaline with Zn sodium hydroxide solution to Brilliaatgelb and a solution of 22 parts of Hatrittosulfidlcristallen in 50 parts water is added. The solution is ^{stirred for 3 hours at 60-65 0} C and then cooled to 20 ° C o The pH is adjusted by adding a dilute hydrochloric acid is adjusted to 7.0, and ee are ropes 150 sodium chloride. the precipitated material is filtered off and redissolved in 1000 ropes water of 4O ⁰ C, umhydroxydlöeung whereupon the pH by addition of a dilute lati ^ adjusted to 11-12 " the filtered solution is "SaIaaäure it again adjusted to pH 7 _f 0 and the intermediate product is precipitated bit 250 parts sodium chloride, filtered off and dried" the Parbstoff can be prepared by the method described in example 19 to applied a woolen fabric

109 84 0/1663

-7t -

* Bs a Klane coloration with a good Waeoheohthelt will be obtained

Example 24

A solution of 2.9 parts of the sodium salt of 1- (2 ' _f 5'-dichloro-4 ^l -bulfophenyl) -> - n »thyl - 4 - (3 ^M -ainlnoplienylazo) -5-pyraaolone in a mixture from 100 parts of acetone and 100 parts of water is ^{stirred at 0-5 0} G, and 1.2 parts of pentadienoyl chloride in 7 parts of toluene are added over the course of 10 aiii, during which the pH is adjusted by adding 9.5 parts of a 2N aqueous solution of sodium carbonate 7 and 6 is held α 20 parts of sodium chloride are added, and after most of the acetone evaporates off ec. has been left, the product is filtered off and dried «.

The dye is applied by the method described in Example 5 to a Hylon 66 Textilßtoff _o Ee is obtained a bright-yellow color, which showed a very good fastness to washing Löeungamitteln xmä

Example 25 Sine solution of 2.2 parts of the Hatriustaalses of 4-Hydroxy-

5- (4 '~ 8 ~ aminoathylsulfai ^^

sulfonic acid in a mixture; «As 100 parts Waeeer and 100

Parts of acetone are ^{stirred at 0-5 0} C, and 2.4 parts of penta

109840/1663

Dienoylochloride in 14 parts of toluene are added over the course of 10 minutes, during which the pH is maintained between 10 and 11 with the addition of an aqueous sodium hydroxide solution. 25 parts Sodium chloride are added -and after the largest rope the acetone has been allowed to evaporate »becomes the product filtered off, washed with a 20 # saline solution and dried «,

When the dye is obtained by following the procedure of Example 5 built nylon 66 tertile fabric is applied, becomes a Obtained bluish-red coloration, which has a very good fastness to washing and sweating

Example 26

Bine lid solution of 6.1 parts of 3- (4 ^l '-Acetylaminophenylsulfamyl) -anilln in 50 ropes of water, 50 parts of glacial acetic acid and 6 parts of 36 # aqueous balic acid is ^{stirred at 0-5 0} C and by adding a solution of 1.4 parts of sodium nitrite in 10 parts of water are added. A solution of 5-6 parts of the sodium salt of 2-amino-8-naphthol-6-sulfonic acid in 100 parts of water is added to the stirred DiaaolÖBung ^{at 0.5 0 O over 20 minutes} . After a 2 3t continuous stirring at 0-5 ⁰ C. 50 parts of sodium chloride are added, Bas product is filtered off, washed with brine and 10biger getrocknetο

109840/1663

A solution of 7.2 parts of the above in 100 Acetylaminofarbstoffs ropes water and 20 parts of aqueous hydrochloric acid 2η 12 st at 90-95 ⁰ ₀ Cf stirred Aminofarbstoff The insoluble is filtered off and dried

A solution of 2 "5 ropes of Natriumsalaes of Aminofarb- = substance in 100! 100 parts of water and acetone -is ropes stirred at 0-5 ⁰ C» and 2 _e 4 parts Pentadiencylchlorid in 15 parts of toluene are added during 15.min, while the pH is kept between 7 and 8 by adding an aqueous sodium carbonate solution ο 25 parts of sodium chloride are added and after the acetone has been allowed to evaporate, the product is filtered off and dried

If it's on a twisted knitted Hylon-6 fabric is applied by the procedure of Example 5, then a red dye is obtained which is resistant to solvent extraction, Sweating and washing one; shows very good authenticity

The following table gives further examples of dyes according to the invention * those obtained by converting the in the second column specified. Amino group-containing dye with the in the acid chloride given in the third column is similar Procedures can be obtained in the previous examples

109840/1663

4 Ms 8 ₉ 16, 18 _P 24 »25 and 26 are described.

You four fairy column of the table will indicate the shade received is when the dyes on the JextΠ materials indicated in the fifth column by that in the sixth Procedure indicated in column ο

109840/1663

Beiep * 27 1- (2'-chlorophenyl) -3-methyl »* PezitadicmoyXehlorid splendid

4 (3 '^ J! & No-6 ^s -stuL £ ophenylazo- · greenish- Beisp «

5-pyrazolone yellow 5

28 "Sorboyl chloride." "» ■

29 1- (2'-Chlorophenyl) -3-methyl-5 (4 * -amino-2 ^$ - eulfopheaylas

30 1- (2'-chloropheayl) -3-

^. methyl «* 4 - '(3 ^l -amino-6 ^l -

a sulfophenylazo) -5-pyra2olone

to ■■■■ '■. ■ ■ ·' '

oar 31 2- (2 * -Methyl-4'-aminophenyl-

⁴ ^ aao) -naphthalene-4,8-disulfone-

5. sawe

co 32 4-hydroxy-5- (3 ^t -aminophenyl-

cn azo) -6-aminonaphthalene-2-

ci) sulfonic acid

33 4-Hydroxy-5 (2 ^L -chloro-4'-aminophenylazo) -6-aminonaphthalene-2-sulfonic acid

34 4-Hydroxy-5 (2'-PhOHyIBUIfamyl) 4 ^l -aminophenylazo) -6-

acid

Pentaienoyl chloride rStlich- Il it 1769205 2-cyano sorboyl-
chloride yellow ti » Pentadieuoylchlorld yellow tree
wool how
Beiap
7th Pentaalenoyl chloride yellowish
Red Nylon-6 much
Ex
5 Il bluish-
Red Hylon-66 Il «I. magenta-
Red Il Il

4-Hydroxy-5 (3'-ß-aminoätbylsttlfa ^ jrlphenylazo-) ·· = · 6-aminonaphthalene-2-sulfonic acid

BsJitadienoyXchloride red

4-hydroxy-5- (4 * -chloro-5'-ß-amluoethylsulfamylphenylazo ) —E — aininoiiaplitha— lin-2-sulfonic acid

37

38

yy5r3 ( metliylaminophenylsiilfasayl) phexiylazol-6-amin.onaphthalin-2-8ulfonic acid

45ydroxy5r3 (3amiiio phenylsulfamyl) pb.enylazoj -6 amlnonaphthalln — 2 — sulfone— acid

4-hydroxy-5- (4 ¹ -ohlor-

phenylazo) -6-ß-aminoätiiylijoitlliHlfa

4-ΪΤ3ΓΓ! -rr.xy-5- (4 '-amino-

) —6 — amiü.0

41

I / ^ y4 (3

-ö " ⁵ -sulf ophoiiylazo)" 5 "-pyrazolon ~ 1"-yljbenziditi-2,2' -d: I ctilfonic acid wool

yellowish red

like example 5

like example 19

like example 5

bluish red

matt b
licli-red

yellow cotton like example 7

to 00

J 0 **
3ö cn

4-Hydro ^ ~ 5 "(4 ^s -ainiBO-2 ^f -sulfoplie; nyla3O ~ 6« · amiiionaphtlialin-2 * · Bul-

Pentadienoyl * chloride

- Wool

1- (4 ^a - *

44 \ '4-Hy4rwEy->

- (2

fonaäure

4-hydroxy-5 - * (4 * -ainlQO'- y

ph.enylaao) -6 ~ amino chloride

naphthalen-2-sulfonic acid

IC ^ '- Apy)! methyl-4 ~ {4 ⁵ -H-nethyl- N-β-cyanoethylamino- ■ biid5l

Pentadienoyl chloride

Red

yellow

1 - (4-aminophenyl ^E) -3 ^

methjrl-4- ( ? '^ siiü.f ophenyl azo ) -5-pyraaolone.

48

meth.ylr4- (3 '-sulfophenyla'ao) -5-pyrazoloa

t ^ f 3'-

-sulfo-

pjy) 3wy4

12 ' -ßUlf opheaylazo) -5-

pyraaülon

nylon

Wool

cotton

like in «r? piel 5

■ as with «

ΠϊιΙ θ

like example 5

like example

like example 5

like example 7

Beipp. 50 i-

. . '- Pentadienoyleuifophenyi) -3-methyl-4-chloride
phenylazo-5-pyrazolone

yellow

51 copper complex of 6-amino-1-hydroxy-r2- ( 2 "-hydroay-5'-aulfophenylazo / naphthalene-3-8ulfonic acid

Sorboyl chloride ruby

Wool

Baxua - wool

like example 19

vile B

game 7

52 1t2 ghrome complex of
carboxyphenyla ^ o / - Pentadienoyl
chloride Sorboyl chloride Brown Ii tf 53 1: 2 — cobalt complex of
1- (4'-aminophenyl) -3-
methyl — 4— (2 — carboxy — 5—
aulfophenylazo) -5-
pyrazolone Il Pentadienoyl
chloride dull yellow Il ti 54 1-amino-4- (3 '-amino-2' -, Sorboyl chloride 2-cyanosorboyl
chloride reddish
blue Nylon-β as in·
game 5 anthraquinone-2-sulfonic acid 1 -amino-'4- (4 * -ar1 noanilino) -pentadienoyl-
anthraquinone-2-sulfonic acid chloi-ia Sorboyl chloride grimly
blue ti 55 -dto ~ η H Il 56 1-amino-4- (4'-methyl-
amino-anilino) anthrachi-
non-2-sulfonic acid reddish
blue viscose
silk as in
game 7 57 -dto- reddish
blue nylon as in
game 5 58 -dto- Il Il 59

Example 60

OO ■ ΡΙΟ

64 65

1-Alaino-4- (3 '-aetiiyl aminoanilino ) anihra chlnon-2-sulfonic acid

Pentadienoyl chloride reddish

1 — Amino — 4— (4 ¹ —sunio.0— Pentadienoyl— ρ τ τΙΛΙ «<!> ■) —an * fth y fl.ftMi» τ on chloride 2,2'-dL-sulfonic acid blue

1 — Amino — 4— (4'— amino— aniline) anthraquinone

1-Amino-4 ~ (4 '-msty aminoanilino) anthra quinone-2 _t 2 ^! -di-sulfonic acid

. -dto-

1-Amino-4- (5'-amino- « ⁱ 6 ⁱ ithl

, 4 »y anil ino ) anthr aquinone-2,35 · di-sulfonic acid

r> f \ \

4— (4 ^J —ainino— i)

quinone-2-sulfonic acid

1-Amino-4- (4 ^! -Ss-amiaoethylanilino) anthracbinone-2-sulfonic acid

SB i-Amino-4- (4 ^l -β-aniinoethoxyanilino) anthraquinone-2-sulfonic acid

Sorboyl chloride

T ⁱ c> Vi -rr · »W -ϊ /

chloride .- ην.

Sorboyl chloride '" Pentadienoylchlo- reddish-

rid blue

! Tylon

Wool

ti ..

Wool

apiol 5

as in-

spisl 19

; d.s Bsi-

Example 19

10984071663

BATH ORIGINAL

5 rf US '

1098 4Q / 1663

Il

te

Example 86 3.64 ropes

amino) äthylamid «earth by the procedure of Example 3 diaeotiert. To the stirred DiaeolÖsung which is obtained in the "Ueiee, a LBeung during 10 'at 0-5 ⁰ C in toh 2.39 parts of a-Anino-e-naphthöl-e-Bulfonßäurc in 35 water * file that 1, Contains 6 parts of sodium carbonate, suggests that stirring for 15 minutes the pH is raised to 5 by adding an aqueous solution of acetate, and after further stirring for 2 ot the product is filtered off, washed with 2 × 2 sodium chloride solution and purified by dissolving it in a mixture of 600 parts water and 120 parts acetone and precipitating with 20 parts sodium chloride. Bae product, is collected and dried in a Valcuumex Biooator.

Instead of the 3.64 parts of 4-AidJio-2,5-diahlobenzenesulfon-IJ (ßpentadienoyl) -äthylamid, which was used in the above example, 3.78 parts of ^ Aaino-a ^ -diclilorobenzolsulfon-NCßsorboylamino) ethylaid are used.

The pentadienoylamino or sorboylamino dyes that are obtained in this way know on nylon-6 textile or on a serge textile made of merino wool by applying the method described in Example 5 "whereby blue-red shades with good fastness to Schwitssen and Boh ^ feaWaeohen are received » -"? '.- ■■ .'-.'-. "■■ ■ ·

ORIGINAL INSPECTED

Example Q 3.64 parts

Aminoethyl) amide are diazotized by the method of Example 5 «You diazo solution, which is obtained in the d ± 3se manner, is converted into a stirred solution of 2.59 parts of N-ß-sulfatoethyl-iT-ethylHB-tQluidin in a for 15 min Mixture of 25 parts of Vfaeser and 3 »5 parts "*> 6fii.gßT aqueous hydrochloric acid added at 5 ° C * After stirring for 15 minutes, the pH of the mixture is increased to 5 by adding an aqueous Ifodium acetate solution "and that The mixture is stirred for 16 hours at room temperature. The product is filtered off and washed with 5% sodium chloride solution containing a little sodium carbonate. The dye is collected and dried in a vacuum desiccator.

The pentadienoylamino dye thus obtained can by the procedure described in Example 5 on a

^ Hylon-6 textile fabric will be applied »It will be a splendidly W .

red color with good fastness to sweating and

obtained from sharp washing.

V / hen the 4 parts of the Kylon-6-Textllstoi'fs by 4 parts of a serge fabric Merino replaced _v is then obtained a red dyeing with good üJchtheit opposite 3ehwit & s and washing

109840/1663

_s . BATH ORIGINAL

V Example 88

: 'i A solution whom * 5 36 parts of S-Pentaaienoylaminoanilin-ö-sulfonic

¹ I ■ ■ ■ ■ - ■ ■ * '' ■

(acid in a mixture of 100 ropes of water and 7 parts

\ 36 ^ iger hydrochloric acid, which contains 0.1 part of hydroquinone, is used in

\ . ■■ · ■ ■. ■ '.- ■' .-:

I a temperature below 5 ⁰ C by adding a solution of 1.4 % _:. ■. ■ ■ '■' ■

i parts of sodium nitrate in 10 parts of what is diaaotierte the

the diazo suspension obtained in this way is added for 10 min I a stirred solution of 4 * 2 ropes 1 ~ {2 ^ -Ghlorojphenyl-J-

methyl-5-pyrasolone in 130 parts of Waeser, which contains 2 ₉ 12 parts of sodium carbonate and 0 ₉ O parts of hatric acid hydrate added at 5 ° C., the alfcalinity being added by adding aqueous

JCTatriumcarbonsitlösung opposite brilliant yellow maintained ■ \ is ο The mixture is stirred for 4 st ^ and the product is filtered abj, mil; 5 # Koehaalzlösung washed and dried in a ι Takuumexsiccator »

/ The ^ used in the example above

} € «Sulphonic acid is obtained by acylation of 2,4-diaminobenzene

: sulfonic acid with pentadienoyl chloride ±? .. T-racial acetone solution

j received ^

(The dye obtained in this way is

* ■ ■ ■

I bulged Ny: torL - 66 fabric by: ii the same as in Example 5

'beme procedure appropriate, it will be ice-ie gorgeous' gi-usual'

{yellow Eärbsusg eriialteni the one voeaiigXieh ^ authenticity against-

ι Ifesr washing owns

ßAö ORIGINAL

Example 89

A solution -yen 3 » 7 parts.
acid in 100 parts of water and 3 Teilaa 36 $ aqueous hydrochloric acid is stirred at 0-5 ⁰ and G by adding a solution of 0.7 hone Natrlumnitrit in 5 parts of U? .sser diaaotierto

A solution of 2.8! Parts of Hatriurcsalzes of 2-Αιη1ηο · "3" naphthol-6-sulfonBäure in 100 parts of water -is wöhrand 20 min ^ suag zugesetst at 0-5 ⁰ C of geiiöirten diazole ,, After further stirring eineia during 3 st willia 5'- ^! Add sodium chloride to EaB product is filtered off ₃ , washed with 10% sodium chloride solution and dried *

The product is applied to a woolen textile by the Yeffalixen ron example 19. A red color is obtained, which has a good authenticity against u ^^ Schwitaen. V '.'. Id Vfascb.sa ze igt ο

Example .90 _; A solution of LB parts of metb.ylaiaisso} anil: Ld in 50 parts of lis © e.; Ig \ md 2 ■ aqueous hydrochloric acid is carried out at 0.5 ° C. durcl

a solution of 0.35 parts Bfettriusärutrit -ia 2 _? 5 parts water

BATH ORIGINAL

Bine solution of 1.4 parts of 2-dee lfatriumsalsee Aoino-e * · naphthDl-6-sulf oneäure in 100 parts Waaaer is "ghrend SO ain at 0-5 ⁰ C the stirred DiasolÖaung added" After. During stirring for 3 hours, 2 parts of leatriumchlorld are added, the product is filtered off, old 10biger Kooneal solution is washed and dried.

Daa aniline-2-eTjafcfn (4 '- pentadienoyl-rr-methylaniino) anilide _t the Λ

The above example has been used »has a SobÄel point VOKi 175-> 6 ° Co Se is obtained by salaic acid hydrolysis of Hitrobenesol * 2-sulfone (4'-aoetyl'-ir-inethylamino) anilide and ansohliefleole Aoylierting the resulting Nitroben2Ol-2-3ulfon (4'- I-4 "thyl ^ amino) anilide with pentadienoylochloride in aqueous aoeton solution at χιΞ 7-8 and obtained by iron reduction the resulting Vitro * beneol-2-milfon (4 ^l -pentadienoyl" N - metliylaiisino) anilide "

The product is applied to nylon 66 TerbilBtoff by the procedure of Example 5 =, Bs becomes a bluish-red color get »very good authenticity towards Sohwitaen and Prefers to wash »

Example 91

Instead of the 1.8 ropes of aniline "-2-bulfone" - (4 ^l -pentejdienoyl * * -ethylamino) anilide, which was used in Example 70, 1.8 ropes of aniline-2-sulfone (4'-pentadienoyl- N-methyl-

109840/1663 '"

amino) -H - »ethylanilide used, being a dye old Hhn ~ borrowed properties is obtained,

The above in Example · verwendet9 aniline-2-sulfonic {4'-pent5idienoyl-N-methylaminoJ-N-niethylanilid besitat a Schmela · point of 113-4 ⁰ Oa Bs is Durah methylation of Nitrobenaol-2 "e \ alfon (4 ^l "pentadienoyl ~ Nn" thylaiaino) aiidlid with Dirnethylsulfat In aqueous NatriiinhydroxydlSsung and Sisenredüktion dos resulting HitrobenBol ~ 2 "* eulfon (4'-N-pentadieiioyl ~ möthylamino) -N-methylanilide received _0th

The dye thus obtained can be applied to a Wollet ext Hat off by the method of Example 5. the · Be will have a bluish-red color with very good bohtheite-neo-like properties compared to vases «

W. A solution of 1.96 parts of '^ -Aoetylaiainoanilin-6-8ulfoiiaä \ rre

and 0.7 parts of Hatritaooitrite in 100 parts of water is given to a Geoiech from 100 ropes of Biewaeser and 5.5 parts of 36% aqueous Balseaur® below S ⁰ O. The diaso suspension hardened in this way is mixed with a cooled solution of 3% SI fellen 1-N-Paatadienoyl8iaino-8-naphthol-3,6-clistilfons & ure in ^ CO ropes water below 5 ⁰ C added. Slowly adjust the pH of the chemical by adding an aqueous sodium hydroxide solution.

109840/1663 -

increased to 6-7 during the second half, the product becomes precipitated by the addition of -.- 2O! dents of sodium chloride, filtered and washed with saline. The product is filtered through Dissolve in 200 parts of water and precipitate by adding 20 ropes of sodium chloride, purified * and filtered with Brine washed- * The product is at room temperature dried in vacuum «The 1-W-Pe ^ ntadienoylaiaino - 8-« naphthol-3 »& - ' disulfonic acid is obtained in the following way?

7-22 ropes of 1-amino-8-naphthol-3,6-clisx; lfonic acid are dissolved in a mixture of 114 parts of water and 80 parts of acetone, which contains 5 parts of sodium acetate crystals, and 1.5. Parts of sodium carbonate and 3 parts Pentadienoylchlorid during 5 min below 10 ⁰ C was added _0th The resulting mixture is then stirred at 20 ⁰ O until most of the acetone is evaporated and the product is precipitated by addition of 20 Teilen.Kaliumchlorid "The product is then stirred at 2O 2 st ° C, filtered and dried at 40 ⁰ C dried.

The dye is applied to a woolen textile fabric by the method of Example 5, a bright red dyeing with very good resistance to washing and potty is obtained.

The following table gives further examples of inventive vessels Aao dyes, which are tind by diazotizing the primary aromatic amines indicated in the next column

Coupling of the Biazo connections thus obtained with the in the

coupling components indicated in the third column are obtained ^ where the primary amine and / or the coupling component contain at least one group of the formula I with one another. The processes used are similar to those described in the preceding examples, such as Z ₀ B ₀ 2 _r 3 and 86-92 became.,

The fourth column of the label shows the shades that are received be when the! textile fabric e on d: Le in. the fifth column specified sextile materials are applied by the methods specified in the last column,

1663:

BAD ORlG (NAI.

Beiep, 93> -Sor1) oylairdnoaiiiliii-6-erulfonic acid

^ -y aniline-6-sulfonic acid

"

1- (2'-Chloraphenyl) - splendid nylon-6 like Example 5 > -methyl ~ 5-pyraaolone greenish yellow

2 ~ H ~ methylamino-8 wool "

naphthol-6-sulfonic acid red

1-acetylamino-8- bluish- ""

napfethol-Sfö-disul- * red

fonic acid

M. 1 -Pent adienoylataino-
G-iiaph1; liioX-3i 6-disul-
ionic acid Red Tree-
full like example 7th CO 97 M. Red Wool like example 5 CD 98 4-pentad ± enoylainino-
2,6-diehloraniliJi 2-amino-8-naphthol-
6-sulionic acid Red Hylon-6 11 O
Oil 99 1 _f 2 _P 4-thiadiaaol methyl-N * -sorboyl- Red Hylon like example 1 · ^:
U 100 2 * .ÄndaoljenethiaeoX n bluish- η η Red 101 ^ -Pentadlenoylaiaino- 1- (2S5 ^f -Biciaoro- yellow Wool like example ' t9 PfI ^ I ι y ^ aAr ^ «af4 ^ I T iiyi KHJl ^ H ethyl-i-pyarazolone 102 M. 1-phenyl-5-methyl- yellow ti like example 5 105 H 2-4iaphthylaraln-6-
eulfona acid orange « η 104 ? e tree
wool like example uaphthol-7-SAalfoneätu

- 92 - Example

O, 4th Parts 37, 4th It 2, 4th Il 18th Il 12th Il 1 > It

The pentadienoyl dye of Example! 57 is prepared according to fol The following approach is incorporated into a printing paste:

Dye water ammonium sulfate Emulsion thickener

Modified thickener made from legume bean gum (known as
Indalca PA5) 9? Solution

Di ~ tert ~ butyl diperphthalate

The printing paste thus prepared is applied to a bulked nylon 66 fabric, and the fabric is "suspended at room temperature for drying He is then 30 aiin steamed at 102 ⁰ O and is wound complete and 10 min at 6O ⁰ C in a solution of 2 parts of a non-ionic detergent in 1000 parts Walser washed "the dried fabric is printed with a bluing hue ¥ a very good fastness to extraction with a solution of pyridine in water and gegenüliar the iOS o- _n ^:: 5- ashtest has ο ^{s li}

Example 106

I am bleached BaurawOlltextilstoff wircl through a solution of 1 part of di-tert-butyl diperphthalate in 10O parts of acetone It is allowed to dry -and is then through

109840 / T663

BATH ORIGINAL

a solution of 1 part of the dye pzOd-ukts from Example 57 and 10 parts. Urea »dissolved in 1OC parts. Water _p "out -hinduroh" The fabric is zxxr remove excess expressed liquid, dried tuid then 10 min steamed at 102 ⁰ O "It is finally 10 min at 100 ⁰ C in a solution of 2 ropes of a non-ionic detergent in 1000 Share water washed **

The dried textile is dyed in a reddish-blue shade with good washfastness.

Example 107

The pent adlenoyl dye product yoa. Example T is applied to polypropylene yarn (trade name "UXstron") by a dyeing process similar to that of Example 1 for cellulose triacetate fabric. There is obtained a yellow color and a substantial * * Percentage of the dye remaining after extraction with pyridine in a Soxhlet Bxtraktionsapparat on the fiber "linaaii dor £ ^r OL3 merisations-ini.tiator is omitted, diirch DIE solvent extraction, the entire Removed stain from polypropylene fiber

109 840/1663

Example 108

0.02 parts of the pentadienoyl ^{dyestuff pr3c:} ukts τοπ 3eispisl 1 are finely dispersed in a dyebath, the 50 parts of water 0.15 parts of potassium dihydrogenphosphai; *: / l contains 0.075 part of the disodium salt of methylenedimphtiiallnoulfonic acid, 2 parts of polyethylene terephthalatex ^! .; ili;:; off are ^{dyed in this dyebath for 30 min at W 0} C ο De :: · Textile is washed in hot water and rinsed

He is then passed through a solution of O ₃ * Share Benr-; let oyl ^ ero .yd in 30 parts of acetone passed uiül dry ^ uaä then 5 gtidämpft min at 165 ⁰ C at atmospheric pressure - The fabric?. will end up 10 me. l: oi 60 C in a solution 2 parts of an synthetic non-ionic Dstergenzas washed in 1000 parts of water "rinsed rad dried ·, It is dyed in a yellow yellow shade _for " an excellent fastness to extraction with byridine and to einam dry hot bleaching test, which executes fZ nc, n at 2 * Ό 0} :. r ·; will »owns ο

The authenticity to eyridine and to V. ^r Sr.n & xst tessar as "with a similar coloration" in df: -? Ciie Benaoylperoagrd treatment has been omitted ₃

BATH ORIGINAL

-. ^ • j ΐίύ »:

Example 109

5 ropes of a bulky Hylon 66 Tezt fabric, known in trade as "Sanlon", «ground into a dye bath containing 0.025 parts of the Pentadienoyifarbetoffβ Tem Example 5, 150 parts of water, 0.1 part of oleyl sodium sulfate and 0 , 15 ropes Aamohiumacetat contains "Bas dyebath is stirred and its Hesiperatttr is increased to 100 ° and 0 JO min maintained at 100 ⁰ O. Mused "earthed 0.3 parts of acetic acid indicated, and the dye bath is maintained for a further 15 min at 10O ⁰ C; The nylon fabric is dyed in a bläulioh-red hue, and rinsed in water at 60 ⁰ C and dried *

The dyed nylon textile is then exposed to the radiation from an X-ray tube which has a chrooeohint and operates at a stroke of 5K and a voltage of 45 kV. The radiation lasts 5 bin It is found that, in comparison with the non-irradiated area, it has a much greater fastness to interfering action with a boiling solution of 50 parts of pyridine and 150 parts of water.

Example 110

The dyed nylon fabric of Example 109, which has not been irradiated, is exposed for 20 seconds in a vacuum to a Klektronatjet, which with an emission rotated voltage of 2.5V,

109840/1663

an acceleration voltage of 60 Jcv and a non-radiation current vfcn 30fi A "

The irradiated Plächo changes its part to a bluer hue, and it is found that in comparison with the nioht irradiated Pläöhe a much higher authenticity compared to extraction with a boiling solution of 50 ropes of pyridine and Has 150 ropes of water »

Example 111

Bine Lorning vöa 10 parts · ^ -Pentadienoylaminophenylaaoaceto- aoetanilid (prepared from the corresponding Aminoazcrverbiadung duroh acylation old Pantadienoylohlorid using Method E of Example 1) in 200 parts of diethylene glycol dimethyl ether is added with stirring uodestilliertea vfihrend 1 et a »f erhitat 130 ⁰ C and 3 st held at 130 ¹⁰ O • The polymerisation is pursued duroh ation chromatography, and a Near-»au vouet & idige shows conversion to polymer The polymer _c \ rird then duroh addition of petroleum ether (60-80 ⁰ C) was isolated. The resulting product is suitable after a suitable treatment, such as "Bo a solvent ball milling, for incorporation into plastics, such as Sr.Bη in polyethylene", whereby yellow shades are obtained with good waterproofness.

109840/1663

Example 112

Polyethylene terephthalate staple fiber TextU.stoff is made with a Printing paste printed, which have been produced according to the following approach is:

g aqueous dispersion of the pentadienoylamino dye Q from Example 1, 3 parts

jg (weight / weight) sodium alginate solutionj, commercially available as "MMÜTEK P" (Alginate Industries Ld) is available

2 # (weight / volume) aqueous bensoyl peroxide dispersion . 3 »5

Irisacryloylhexahydro-s-triaain O »5

(The aqueous dispersions are made by grinding on a ball with the appropriate amount of solid and water and with 4 parts of the disodium salt of methylenedinaphthalene sulfon " acid produced) ο

Ber bedraekte fabric is getroclmet in air at 5O ° O and ά & ηη 1 min "at 200 ⁰ C gebaekeno Br is then washed at 60 ⁰ C for 10 min in a solution containing 2 parts of a non-ioni" see detergent per 1000 parts of water contains _s and dried

A yellow print is obtained which, compared to a print made from the same printing paste by which the lensjoylperoxyd or the Tris-aeryloyl-hejcahydro ^ s-

have been omitted »a lesser authenticity would-extraction with boiling pyridine

Claims (1)

contain, in which fi is a hydrogen atom or a substituted or unsubstituted alkyl, aryl or ATal & yl radical, R. is a water et off * © or or an alkyl * or Gya & oradikal, independently of one another a hydrogen or or an AHeylradSJc & l represent iaad Ee eia or Halogenatoa or a Söhl @ sfwasserBi ^) ff represents radical, with a ^ Me the
directly with something present in the dye
is feuipft. Contains 4 carbon units a _c . ae 1 ο h Ti θ%, & a & S ₁ , R _gr t ^ "iU . . -. 99V ο dyes according to one of claims 1 to 3 »thereby g a k e η η ζ e 1 ch ß β t that they per dye ££ molecular one or two groups of the formula - ν - oo - ο * σ - c »< R 'R ₄ Ro Rl R4 where R "H, R", B-, R. and Re contain those in claim 1 have given meanings, ο dyes according to one of claims 1 to 4 »thereby gekennae declines that they are members of the Azo, anthraquinone, phthalooyanine or methine series are * 6 “Dyes according to one of claims 1 to 5 t d ad u r c h g e k e indicates that they have at least one contain water-soluble group per molecule. 7 «dyes which contain at least one group of the formula RR ₁ R ₂ en1dialten _f in which R, R ^, Rg, R-, R ^ and R ^ have the meanings given in claim 1 and each of the groups mentioned are linked to a carbon atom present in the dye with the aid of an SOg grouping _o 10984Π / 1663 Ί769205 8. Dyes according to claim 7, characterized in that R ₁ , E ₂ , Ry R and R, - each mean hydrogen » 9ο dyes according to one of claims 7 or 8, characterized characterized that ax per dye molecule one or two groups of the formula I ■ / H ₅ k JLJLl \ contain, in which R, R ₁ , R «» R «, R ₄ ^ nd R, - have the meanings given in claim 1» 10 «. Dyes according to one of claims 7 to 9 »characterized in that β ie members of the azo, anthraquinone or phthalocyanine series are _o Dyes according to one of Claims 7 to 10, characterized in that they contain at least one water-solubilizing group per molecule _o 12o method for the production of those specified in claim 1 Dyes ,, characterized by that one has a dye compound, d: ie at least one group the formula ;; -HHR contains, wherein R has the meaning given in claim 1 possesses, with an acylating agent _s the introduction 109840/1663 - 101 of a radical of the formula / ³ p co - o »σ ~ c ■« ο ^ wherein R. _f R ₀ "R ₃₅ R ^ and R _{5 have} the meanings given in claim j, is suitable, -reacts" 13. Process according to claim 12, characterized in that the acyl chloride is an acid chloride uses i-drd » 14 ο Method according to claim 13, characterized in that the acid chloride used is pentadienoyl chloride 15o A method according to any one of claims to 14 »characterized GEK eη aeich η η t e 12 that cie Parbstoffverbindung a member of the azo, anthraquinone - ,, PhtheXocyanin- or methine isto β A method for the division of the perfume substances according to claim 7, characterized in that η ζ eich η et,; let a perfume substance: rl> indung the at least one group of the formula in which Il the: stated in claim 1. "Bedet?: '.; ung owns, contains »with an acylation agent:., the aur introduction 109840/1663 ORIGINAL • 102 of a radical of the formal -CO -CaC- ^R 1 Kg ^R 3 ^R 4 wherein R ^, Rg ₁ - R * »R ^ and R, - have the meanings given in claim 1, is capable of converting * _fc 17 »Process according to claim 16, characterized in that» an acid chloride is used as the acyl chloride » 18. The method according to claim 17 »characterized in that the acid chloride is pentadienoyl chloride is used" 19o A method according to any one of claims 16 to 18, characterized in that the dye compound is a member of the azo "anthraquinone or Phthaloeyanin- W row © ₀ 20 _β process for the preparation of the dyestuffs according to Claim 1, members of the azo series are "characterized in that the coupling is a Dias compound of a primary amine with a coupling component" wherein the primary amine and the coupling component together at least one group of the formula 109840/1663 ■■ - If - CO - C - -C - C-β Q ^ R. AA I - \ r ■ " ^K 1 ^Κ 2 3 4 included, νοτχη. R, R ₁ , R ₀ , R », R _A and Rr have the meanings given in the claim, β Method according to claim 20, since el urchgeke η η ζ ei ο h η et _f that R ₁ , R _P , R · ^. » R /. and R ₁ - each denotes hydrogen _c J 22ο Process for the preparation of the dyes of claim X ₉ which are members of the Phthalocyanin- odor Anihrachinonreihe, characterized in that a phthalocyanine or anthraquinone dye compound, which contains at least one sulfonic chloride group, is lynsetst with a compound which has a primary or secondary amino group in addition to a group dsr formula 2 ^ 4 wherein R, R ^ _f Rg, R ,, R ^, and R ^ have the meanings given in claim 1, implements. 23η method sur production of dyes that at least a group of the formula 10984Π / 166 3 BATH ORIGINAL . ,, fi., CO - G m C ~ C «O '
! til ^v -.- RTJ "D τ ;. ^a i,"C; contain »where R, R ^, R ₂ » R ^, R ^ '^ d Rc have the meanings given in claim 5χ' and Lie group is bound by means of a methylene bridge to an aromatic nucleus , since ü υ. ν chgeke η χι ζ 'i η et that one has a Farbrtofivei bond or e:, r <. .r. ^; i ^! bgtof: Ca pillow product which contains a ο X ^ r several aromatic _E α ctetabare Waaeei * sto:? fatome-exhibiting nuclei, m; .t a lWiethylol- _g li-methylolether- or N-haloE.eth; yl derivative of an amide der formula M-CO-CaC-Ca Of !, ί II, ^N \ I .. R * Rp R ₇ . Λ « ^T rorin R,. ' ■ _£ P- _9f R _7. , R ^ ₁ and R _c c'ie är; imspcu.ch 1 specified Significance own, convert 24c- procedure sur staining of fiber diatoi-ials ode :? Po3.ymeren films, characterized in that scan by means of dyeing, logging or printing processes one or more I: .. rbst-offe according to one of the standards ΐ ois β and applies ■. 109840/1663 ORIGINAL BATHROOM 25o method according to claim 24 »daduroii gikf na · indicates that an agent which can bring about a polymerisation of polymerisable, ethylenically unsaturated compounds is applied to a fiber material or dia
polymeric films apply _β 26 «Method according to claim 25, characterized in that that the agent is a free radical generating compound or the components of a free radical * generating system contains 27 »Method according to claim 24, characterized in that the fiber material or the polymer * meren film after coloring an electron beam or
the irradiation from an ultraviolet, X-ray or
Qanma radiation source exposes 28ο Method according to one of claims 25 or 26 »da - characterized in that the means Λ is used in an amount of 1-500% by weight, based on the dye used, 29 «Method according to one of claims 24 to 28, characterized in that the dye is used together with one or more other compounds that have at least one polymerizable olefinic Group included 10 98 4Π / 1663 toe 30, method & ar coloring of fiber materials or polymeric films, marked thereby 5; eich η et _F that one or more dyes according to one of claims 7 to 11 and o is applied by a dyeing, padding or printing process ο Method according to Claim 30, characterized that an agent capable of polymerizing a polymerizable, ethylenically unsaturated compound is applied to the fiber material or the poly- ■ more film is applied o 0 Process for the production of colored polymers "characterized in that a dye according to one of claims 1 to 6 is polymerized ₀ 33v method according to claim 32, characterized treating the dye with a compound or compounds; those used to generate free radicals are capable » β Method according to one of claims 32 or 33 ·. characterized in that the polymerization is carried out in the absence of a fibrous material or a polymeric film o I ¹ ATINTANWXLTe Ot-INO-H-FlNCKe, DIPL-ING. H. BOHK DIfL-ING. S. STAEGER 109840/1663 BATH ORIGINAL