DE1919595A1 - Coloring process - Google Patents

Description

Folder 21927 - Dr _ö K / hr
Case D.21003

DESCRIPTION UNa for the patent application of

IMPERIAL CHEMICAL INDUSTRIES LIMITED, London / Großbr _c

concerning
¹¹ dyeing process "

Priority: Great Britain from April 17, 1968 No. ₀ 18119/68

The invention relates to a method of dyeing, and in particular on a process for dyeing fiber materials and polymeric films with certain azo dyes «,

According to the invention there is provided a method for dyeing fiber materials or polymeric films proposed, which is carried out by the fact that the fiber material or the polymeric film with a solution or suspension of a monoazo dye the formula

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P - CO - O a CfH,

-la

(I)

treated, in which A is the remainder of a diazo component of Bens ©! -, Naphthalene or house clean represents, E the thatch one in Naphthol coupling component coupling the ortho position, P represents a grouping of the formula -0-, -NH- or -NH-NH-, ζ represents an integer and m an integer having a value of at least 2, after which the treated material or film is subjected to the action of a polymerization catalyst

In the case of the dyes of the formula I, as defined above, each of the groupings represented by P is bound directly to a carbon atom which is present in the dye Form aryl radicals or can form part of an alkyl chain which is either bonded directly to an aryl radical present in the dye or is bonded to the aryl radical through a bridging atom or a bridging group. Examples of such bridging atoms or bridging groups are: -0-, -S-, -NH-, • i-JÜJcyl, -COBH-, -SO ₂ -, -SOgBH- and -SOgN-alkyl.

Each of the groupings represented by P is pre-

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sugtnreiee -MH-. The value of 2 let preferably 1 or 2, and the value of m is preferably 2 or 3o

Particularly suitable dyes of the formula X for use in the present processes _and the following:

(i) dyes of the formula

-SiHCOC «CH ₂

CH ₃

where £ represents the reed of a Methacryloylaminonaphtholßulfoneäxire, vie sB · i-Methacryloylaaiino-e-Haphthol ^ ie-disul · fonic acid, 1-Metnacryloyleanino-8-naphthol-4 , 6-disulfone acid, 2-Hetbacrylo7laadLthno-5 » -Bulfonic acid, 2-methacryloyl-; eniino-8-naphthol-6-3ulfoneäure, 2-Methaorylpylaoino-e-naphthol-5-sulfonic acid & _f 1 Hethacry1oylaaino-5-naphthol-7-eulfonsäure _v 1 '4? ethaeryloylanino <"8-naphthol-4-8ulf onaäure, 1 -Methacryloylamino <-8 ~ naphthol-3 ₁ 5 «disulfonic acid. and 2-methacryloylamino-S °> naphtholr3 ₉ 6 - di8ulfoneäiH ^> e «The methacryloylamino group in Mag B is preferably bonded in the m-position or p-position with an aso group, xaad the ring B can be further substituted, as s“ B _e by chlorine ₉ Hiedrigalkyl-, lower alkoxy, suif oneäure · or £> _o u3fonaaidgruppen

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These dyes can be prepared "that a diazotized aromatic Nitroaiain with a Acetylaminonaphtholkupplungskomionente coupling _v the nitro group reduced, the Acetylamir.ogruppe hydrolyalert and the free amino groups with Mettacrylsäureanhydrid or Methacryloylohlbrid acyl ^ ert" Auer native they can be prepared by reacting a diazotized aromatic acetylaminoamine is coupled with the acetylaminonephthol coupling component, hydrolysed and the free amino groups are aeylated with methacrylic anhydride or methacryloylehlcrid.

(2) (a) Dyes of the formula

^ bVh = H-

"SO ₂ HiIYlIHCOC. = CH ₂

wherein B has the same meaning as in (1) above and Y represents an alkylene, The sulfone-acyl-iminoalkylamide is located in the o-position, m-position or p-position Azo group, and Ri ig B can be further substituted as in (1) above be*

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191S595

These dyes can be prepared by Coupling a nitrobenzenesulfonyl chloride with the corresponding aliphatic diamine, reducing the nitro group with the Methaciyloylaoinonapfctholkupplungsverbindungen couples and with Methacrylic anhydride or methacryloyl chloride acylated to Alternatively, the nitrobenzenesulfone-O-aminoalkylamide can be used with Methacrylic anhydride or methacryloyl chloride acylated, reduced and with the appropriate methacryloylamino coupling component to be coupled »

(b) As (a) with the difference that ϊ = phenylene instead of alkylene »

These dyes can be prepared by a nitrobenzenesulforyl chloride with a monoacetylphenylenediamine converts, reduced, with the acetylaminonaphthol coupling component couples, hydrolyzes and acylated with methacrylic anhydride or methacryloyl chloride

Alternatively, these dyes can be prepared by combining a trobenzenesulfonyl chloride with a monoacetylphenylenediamib. reacting hydrolyzed, acylated with methacrylic anhydride or methacryloyl chloride, and reduced with the Methacryloylamincnaphtholkupplungskomponente kuppelte These dyes may also be prepared by reacting a nitrobenzene sulfonyl chloride with the appropriate Methacryloylaminoanilin, the nitro group is reduced, and the diazotlerte Amiη with the appropriate coupling Methacryloylaminokupplungekomponcnte _o

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19195S5

(3) dyes of the formula

CCQHH

CH ₂ = CCONH

Mt-

--COHR

- B.

CH ₀ «CCQHH

wherein the sulfonyl amino or acylamino group is bonded to ring B in a- or p-position eur aa group, ring B can be further substituted as in (1) above »R represents hydrogen or a lower alkyl and ß the remainder of an acylaminonaphtholsulfonic acid such as Z ₀ B ₀ 1 "(aeyl) aniino-8-naphthol- % 6- ^ disulfonic acid, 1 - (acyl) amino-8-naphthol-4 _a 6-disulfonic acid, 2- (acyl) aid. no-5-naph-s hoi-7-sulfonic acid, 2- (acyl) -aadno-8-

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19195CG

naphthol-6-8ulfonsäu ^ e, 2- (Acy 1) 8mino-8-naphthol "sulfoneäure 5, 1- (acyl) amino" 5 ~ naphthol "-7-sulfonic acid _i 1- (acyl) amino-8-naphthol -4-eulfoneiure _f 1- (Acyl) amino-8 * naphthol-3,5-disulfonic acid and a-.AcylJamino-e-naphthol-J ^ -disulfonic acid, in which each acyl is a methacryloyl or saturated acyl group, 1 or ^ r a Haphtholeulfonsäure such _e B _o 2-Iaphthol-8-Bulfonsiiuxe, 2-5aphthol-7 ~ _f sulfoneäure 1-naphthol-4HBUlfoneäure, 2-Hap'ithol-3 »6-dleulfonsäure, naphthol"? , 6-disulfoneätire, 1-Hapathol-3 »8 ~ dlBUlfonBätire _t 2-naphthol-6,8-dleulfonic acid and i-iiaphthol-S-eulfonic acid

Dieee Parbatoffe can be produced by an aroBatiaches Hitroaain or an aromatic acetyl amino * amine «it reacts, reduced or hydrolyzed and the resulting amino group with a suitable coupling component Bie-bethacryloylaminobenzoyl or benzenesulfonyl chloride or with a Beneoyl- or BenEolsulfonylohlorid with at least ene acylated two amino group precursors, the amino groups sets in freedom and with methacrylic anhydride or Methaoryloylchlorld aoylated

(4) yarbatoffe's formula

X-BHCO-C »

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1. - OCO-C a CH,

CH,

wherein E has the same meaning as in (3) above, X represents an alkylene and the sulfone-di <- (o-acylaminoalkyl) -amide or sulfone-di-CiJ-eoyloxyalkylJ-amide group. in ring B eich is in o->, m- or p-position to the azo group

These dyes can be obtained by a Hitrobenzenesulfonyl chloride is reacted with a di (6J-ecetylaminoalkyl) amine or a dialkanolamine, in the former case hydrolyzed with methacrylic anhydride or methacryloyl chloride acylated, reduced and coupled with the appropriate coupling component.

(5) Porcel dyes

CH,

2 - t

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where t is 1 or 2, E has the same meaning as in (5) above, the methacryloyl group or methnoryloyl groups in the ring L are in the m- or p-position to the sulfonyl group "and the rings G and L optionally have further substituents, such as a _e B _o low ADcyl groups or chlorine, may contain «.

These Parbetoffe can be prepared by the fact that one mono- or dinitro or mono- or the sodium salt. Diacetylaminobenzenesulfinic acid with a 2-nitro or 2 _? 4 ~ Dinitroohlorobenzol converts, any acetylamino groups hydrolyzed, reduced, all amino groups that are not in the ortho position to the sulfonyl groups ^ acylated with methacryleic anhydride or with methacryloyl chloride, the remaining amino group diazo partially and coupled with the suitable coupling component anyway

Specific examples of the monoazo dyes of the formula I which can be used in the process according to the invention,

are:

1 - "Methacryloylamino-? - (? ^V » methacryloylaminophenylazo) -8-

naphthol-3,6-disulfonic acid »

2-Wethaoryloylamino »6- (3 * -methacryloylaminophenylazo) -5r

naphthol-7-sulfonic acid ■>

2-MethacryloylaminO'-6- (4 ⁱ -methacryloyl-2 ¹ -sulfonphenylazo) -

5 »naphthol-7-sulfonic acid.

2-methacryloylaroino-7- (4 ° -methacryloylaminophenylazoJ-Ö-

naphthol-6-sulfonic acid ₀

2-methacryloylamino-7- (4 '~ methacryloylaminophenylazo) -8-

naphthol «5-Btilf onsäir e ο

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2-meth »cryloylaBiino-7- (4 * -methacryloylamino-2 * -sulfophenyl- 1 -Methacryloylamino ~ 7- (3 '-ß-aethacryloylaminoethylsulf anjl-

phenyla2o) -8-naphthol-3 »6-disulfoiieäureo

2-methacryloylamino-6- (4'-ßH-diethacryloylaminoethylB'ulfainyl-

phenylazo) -5-naphthol-7-sulfonic acid «,

2-Methacryloylamino ~ 7-Z2 '~ (4 ^K -niethecryloylaiDinophenyl) -

sulfamylphenylazq / -8-naphthol-6-Bulfoneäiareo

1 -Acetylaaino-7- ^ ί '-i4 ⁿ -methyl-3 ⁿ , 5 ^lf -bi6methacryloylanilno-

benasoleulf onylaminoph.enylazq7-8-iiaphthol-3 »6-dieulfonic acid.

«Y4 * - (3 ⁿ ₉ 5 ^w -l) ismethacryloylaniinobenzoylamino) -

1 ~ acetylamino-7- / 3 '-di-iß-methacryloylaeilnoäthyl) -sulf axayl-

phenylazo7-8-naphthiol-3 * 6-dlsolfonic acido

2-Acetylamino-7-Z2 · - ^! - (ß-iaetliacryloylaininoäthyl) -sulf amyl-

pfaenylazq7-e-naphthiol-6-aulfojisäuree

2-Acetyleunlno-6- _i / 4 -di-Cß-aethacryloyloxyethyl) -sulf amyl-

phenyIa ^ q7-5-naphthol-7-eulfona acid ₀

1- / 4 ^l - (4 "-Methyl-3 ¹¹ , 5"-l> ia- «aethaeryl oylaainotenzenesulfonyl-

aminophenylazq7-2-naphthol-3 ₁ 6-dieulfonic acid "

1 -iiethacryloylaiaino-7- (4 ^l HBethaciyloylamino-2 ⁱ -eulfophenyl-

azo) -8-naphthol-4-sulfonic acid «,

1 -Methacryloylamino-7- (3 '-methaeryloylasainophenylazo) -8-

naphthol-4,6-disulfonic acid _o

1 -Methacryloylamino-6- (5 '-methaeiyloylamino-2' -eulfophenyl-

azo) -5-naptLthol-7-sulfonic acido

1 -Methacryloylee * ino-7 * (4 ^I -ßHoethacrylovlaminoäthylsulf amyl-

phenylazo) -e-aaphthol-4-sulfonic acid.

1 -Jlethacryloylamino -? - / ^ * - (4 ^H -methaeryloylaniinophenyl) -

sulfimylphenylazo7-8 '"naphthol-4 _f 6-disulfonaäU2 * e _e

0 0 * 9 836/2021

1 "Meth & cryloylamino- 5- (3 '-ß-methacryloylamixioäthyleulf amyl"

i> henyla £ o) -5Hoaphtho L-7-sulfone acid «,

1 -Aoetylamino-7 ·· / ^ - U ^w HBethyl-3% 5 "-bisttetbacryloylainino benisolsulfonyland.no) -phenylazq / -8 ~ naphthol-4,6-di8ulfonic acid.

1 «, ^ 4 · - (3", 5 "-BlOTIe ^ b icryloylaminoTbenaoylamino) -phenylazq7-2-

naphthol-8-aulf onaUu? e ₀

\ - / ^ «- (4" ^ iethyl-3 "t 5 ^M -blsmethacryloylaniinoben« olßulfonyl-

amlno) -phony la & qj ~ 2- iaphth hol-7-eulfonic acid _o

2- / 4 · - (3 "15 ^H -Bisme" h loryloylaminobenaoy.laoino) -phenylazq / -

1-naphthol-4-sulfonic acid. . .

t- / 4 · - (4 "-Methyl 1-3" »5" -bismethacryloylscninobenzolBulfonyl-

amino) -phenylaeq7-2-aaphthol-3 , 6-dieulfoneäuro,

2-acetylanino-7- / 4 "- (4" -aethyl-3 ", 5" -bismethacryloylaminobenaol-

eulfonylaalno) -pheay la * q / -8-naphthol-6-aulfonic acid

1 -Acetylanlno-T-ZS '-il- (ß-methaQryloyl8xalnoäthyl) -eulf amyl-

phenyla «o7-8-naphtho1-4-sulfonic acid.

1 -Acetylaalno ^ - / ^ ¹ -ii-iß-methacryloyloxyäthylj-eulf amylphenyl-

azo7 "8 = naphthol-4 _f 6" isulfonic acid.

1 - / 3 * -Di- (ß-methaory Loylamlnoätbyl) -au] .f amylphenylazo7-2-

naphthol-8-Bulf οηΒϋυre.

1 "£ z ^% -Di- (ß-methacryloylaminoethyl) -auJfamylphenylazq /« 2-

naphthol-7-eulfonic acid,

2- / 2 * -Di- (ß-methacry loyloxyethyl) -sulxCJoylphenylazq / -2-naphthol-

4-8ulfonic acid.

^L -btsmethacryloyleittlno ^| - 2-AoetylamiAo-6/2 '(4-methyl-3' i5 ⁿ phenyl) -eulfonylphqnylaBq7-i5-naphthol-7-eulfon86ure, 2-acetylainino-7- / 2 ⁽ - (3 "-aethacryloylaminophenyl) -Bulfonyl-5 '- me thacryloy lamlnophe aylaeo ^ -e-naphthol- -5 -sulfoneäure _o 1 - / 2 '- (4 "-Kethyl-3 * ₁ 5" -biamethacryloylaniinophenyl) -Bulf oayl-

pheny laEo7-2-napht'ic l «« 8-aulf onsftur e.

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1 - (4 * -Methyl-3 ', 5 * -bisinethacryloylaminobenzolsulfonylamino) -7-phenylazo-8-naphthc 1-3 _y 6-disulfonic acid, »

Further classes of substances used in the invention Methods used ν earth are the bismethaoryloyl. analog of the Bisacryüoyliarbötoffe used in the British Patent specification 984 80 * are described «,

Fiber materials dyed by dae erflndungsgeniäase method rounder are z.Bc textile materials, leather and hides leztilmaterialien which are colored in such a way to include both natural and artificial lien such as _o textile materials containing natural cellulose · = "fibers, such ₀ B. Ba ¹ on.wool, flat ₉ jute, hemp ₉ sisal raiä ramie, regenerated cellulose fibers _ff never z _ffl B _o Vlskoserajoa and cupraiamonium rayor.j cellul © 8eeeierfaa © ra ₉ like Z ₀ B ₀ cellulose acetate raad cellulose triacetate, natural Prot® ± afas © Ea ₀ like gB, wool, silk and mohair ,, regeaor: synthetic polyamide fibers, like z, B ₀ • Polyaerylnitrilfase: m, modified Polyaez ^ laitrilfaaesa naadl polyurethane fibers contain en ₀ This materiaüea kösmesi ia 2? © sa of loose fibers , Lucte, yarn or piece goods mere pilme _s that can be dyed ₉ g are polyimide and polyurethane materials

D & 3 dyeing PaeeiTEaterialien or polyiaeren Filme.ι the erfindungegeinässe method can autsgefülart the ₉ tand that applying one or more monoazo dyes of the Pormel I by a dyeing, padding or printing technique thereon the colored material, or the colored film with

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a polymerization catalyst-treated Alternatively, the dye may be the same :: _s eitig be applied with the polymerization catalyst "at a temperature below that of the latter wei;. continuous inactive can ₃ and the catalyst daim followed by heating, steaming or other measures activated / ground _o

In the case of a dyeing process, the polymerization catalyst can be added to the dyeing process> after the dye has largely been completely absorbed by the textile material ₀ Alternatively, a process with two baths can be used, whereby the dyed textile material is transferred from the dyebath into a separate bath what a solution or? Suspension of the polymerisation catalyst contained in water or in an organic solvent, if desired, the treatment with the polymerisation catalyst can be brought to an end by removing the textile material from the solution or suspension containing the polymerisation catalyst, drying it if necessary, and then heating it for storage and / or damping or Anderea treatments is subjected to the catalyst to activate Preferably, should have a temperature in the range of 20 to 200 are adhered to ⁰ G during the treatment of the fabric with learning polymerization catalyst "

In the case of a printing process, the polymerization catalyst can be used together with a monoazo dye of the formula I has been incorporated into a printing paste »which is then on a Textile material can be applied which then

009836/2021 ORIGINAL BATHROOM

the action of V% τηβ and / or steam is exposed to to activate the polymerization catalyst and the dye to fix. Alternatively, a printing paste, i.e. the Contains dye, are applied to a textile material, which is then converted into a hot solution or suspension of the Polymerisatlon3l: a; analyzer is immersed, or that Printed textile material can be impregnated with a solution or suspension of the polymerization catalyst and then impregnated be subjected to the action of V / Ä.ine or steam »

The fabric ha ai with the printing paste erthält one or more of the dyes, by any of the known methods for applying printing pastes on textile material lien be printed, such as, B _o by means of tfalzendruck, screen printing, Blookdruck, injection pressure, and stencil printing ₀ The Printing pastes can also contain the auxiliaries usually used, such as Z ₀ B ₀ urea, thickeners such as ZoB. Ethyl cellulose, starch, locust bean gum, sodium alginate, water-in-oil emulsions, oil-in-water emulsions, surface-active agents, Natriura-m-nitrobenzenesulfonate and organic liquids such as ₀ ethanol «

In the case of padding processes, the textile material can with a Solution or dispersion containing the dye and the polymerization catalyst padded and dried if necessary and then gelated, heated and / or steamed or other treatments interwoven with the catalyst au activate »Altemitiv can activate the textile material with a Solution or dispersion containing the dye, padded, dried, if necessary by heating, again

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with a solution or dispersion of the Polymerieationakatalyeatore padded, possibly dried and then stored, heated and / or pocked or other! treatments for Activation of the catalyst are subjected «,

As the polymerization catalyst is preferably one or more of Freiradil.alerzeugungsmittel or systems used, as ready as initiators for the polymerization of ethylenically unsaturated compounds used ▼ on "Suitable means sine z" _o B: Organic I-he oxy compounds such as ζ. Β »peroxides, fljdroperoxyde, peracids, Pereater and percarbonates such as e ₀ I <> acetyl peroxide, Proplonylperoxyd, benzoyl peroxide, laurcylperoxyd, Stearoylperoxyd> t-butyl peroxide, t-Amylperoxyd, 4 ~ Chl © i ⁵ obe © soylperoxyd _i 2.4 Dlchloro-

Gyclohesanonperoxyd, T @ tralinhydroperoxyd _s t-Butylperbeszoatg, I5i-t-bm% Mlpe? Phthalat, t-'Bis.tylperacetat, PeressigsEnre, Fe ^ feesnsoesais ^ ee gd ^ ameis-isisäurea Biiaopropylperoxydicorbet ^ l madat © s ^ BiLLfoayip © SO3cyd, Azowie s _o B _e 1,1 ⁸ <-As © "© isis © MbyronitI ⁵ Il ₉ 4i4'-

1,1 * -Aaobls-f-eyelopi-opylps ³ ©! I ossit ^ JJ ,, 1,1 ^β -ABobis-1,3-dimethylvaleronitrile, \ nd aaorgaaieeh, ® compounds such as ζ · Β _β hydrogen peroxide, iiasioni% imp @ rEulfat _(? aliump © r sulfate, Uatriumpersulfat, Cex ammonium nitrate and Cerammoniumsulfato Other suitable Prejxadikalerzeugungssystem are, for example, the _o te Redoxsystemec Geeigm reducing agent for use in Redoxsyatemen in \ Getting Connected with suitable oxidizing agents bind ZoBc £ if.en ( II) salts such as Bo s _o Eieen (Il) and -Bulfat EisenClD-ammonitmeulfat, ethylenediaminetetraacetic acid,

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Metal formaldehyde and metal acetaldehyde sulfoxylates, such as sodium dimaldehyde sulfoxylate, sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium thioeulfate, sodium sulfide, sodium hydrogen sulfide, thiohydrogensulfide, thioglycolic acid, thioic acid, oxy-ureaic acid, thioglycolic acid, oxy-oxy-urea, thioglycolic acid, oxy-cyl ureaic acid, ascioic acid, cyanuric acid, thioglycolic acid, oxy-urinic acid and its water-soluble acid. Hydroxylamine salts, such as Z ₀ B ₀ the flydrocnlorid and sulfate, hydrazine, hydrazine salts such as Z ₀ B ₀ the hydrochloride and sulfate d-glucose, dextrin, glyoxal and sulfinic acids and mixed * such agents »Suitable oxidizing agents for use as an oxidizing part of a Redox systems in connection; with the appropriate reducing agent are, for example, tfaseerstcf .'peroxide, ammonium persulfate, sodium per-sulfate, potassium persulfate, sodium permanganate, potassium bromate, potassium chlorate, potassium perchlorate ,. Egg (III) chloride, ethylene dibiguanide complex E. a: iz of triple positive silver and the various organic peroxy compounds listed above »Mixtures of oxidizing agents can be used, and together with the redox systems, smaller amounts of activators for such systems can also be used can be used, such as Z ₀ B ₀ copper sulfate, hydroquinone and silver nitrate

It is also possible to use other compounds which are known to act as initiators for the radical polymerization of ethylenically unsaturated compounds, such as diazonium compounds and stabilized diazonium salts, cobalt complexes such as "dichloroaquotriamminocobalt chloride and trinitrotriamminocobalt, sulfinic acids such as Z ^ B _n benzene and p-Toluolsulfinsäur "transition metal carbonyls, such as _e iolybdäncarbonyl _P cobalt and

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Nickel carbonyls and svar optionally in connection with a phosphine, in connection with an organic halogen-containing compound, such as SeB ₀ carbon tetrachloride, carbon tetrabromo, chloroform, bronioform and N-bromosucciniaide, JJ-hitrosoacylamines, such as Z ₀ B ₀ N-nitrosoaeetanilide, N- Nitroaocarbanilid, F, H ^l -dimethyl-! I, N ^l «dird.trcsoterephthalaffi: ld and H-chloroptoluenesulfonamidο

If desired and when appropriate, the use of chemical means ale free radical generationBsyliterne by the Use of other means for generating free radicals can be supplemented or replaced. For example, a textile material to which a dye according to the invention has been applied can be exposed to radiation, for example from an ultraviolet, x-ray, or ffer Qamma ray source, or with an electron beam,

The suitability of a special polymerization catalyst or catalyst system for use in dyeing, clotting and printing processes depends largely on the application process used, the temperature at which the process is carried out, and also on the textile material which is dyed by the process according to the invention should be, abc This is how it is in the dyeing, printing and pressure application processes in which hydrophobic textile materials are used, such as. Polyethylene terephthalate and Cellulosetriaeetat textile materials, preferably organic peroxy or azo compounds, organic ale polymerization · use PUr nylon "tmddie more hydrophilic textile materials such * B ₀ wool can sod organic © peroxy or organic Aeover-

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19195S5

bindings used in the dyeing, padding and printing processes become »but in a batch-white dyeing process it becomes preferred to use inorganic peroxy compounds such as. e.g. hydrogen peroxide or persulfates and, in particular systems based on hydrogen peroxide and the like like ZoBo potassium or ammonium persulfate.

The most suitable amount-of the used PolyiB © FÄs) at ± ®2is · -katalyeators is preferably in the range tob. 1 to based on the weight of the dye used »

The dyeing process according to the invention results in dyeing. Printings with a remarkable authenticity gegenufeer wet treatments and it can be shown that _P äies .weit «= · extent its cause DE® in the use Polysserisatioa © ·" Catalyst A has. Furthermore, for improved BaSechtlichkeit-. an effect of the polymerization catalyst can be demonstrated by extraction of the dyed textile material or polyamic films, ι resistance to solvent extraction is much higher in materials that have been treated with a polymerization catalyst than the corresponding dyeings or prints where such a treatment has not been carried out.

The process according to the invention is particularly suited to dyeing Cellulose and especially polyamide tex tilmaterialiezi suitable, and the colorations obtained are very high in quality Degree of fixation and fixation excellent authenticity Gegeialifesr nass®. .Treatments from »

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When colors τοη natural and synthetic polyamides, such as B.B · Hylon and Volle, it is preferred to pass the dye through conventional dyeing veil:? drive apply and then after substantially complete absorption of the dye has taken place, dos colored material with the polymerization catalyst either in the same or a separate one Bad su treat «. Ee has been found that the dyes of Formula I, which is not all of two and preferably only one Sulphonic acid group, especially for application to solid and synthetic poly aaidt ext !! materials by the erfIndungsgemäsee Ve: "drive suitable slxul, since they are useful Dyeings with very high resistance to solvents and a number of know treatments result in · They result also surprisingly good coloring properties in terms of their own distribution and control over the world and synthetic polyamides.

If desired, the method according to the invention can be used in The presence of one or more compounds, which contains at least one olefinic group which through a Ffiradl kwi mechanissms is polymerizable or copolymerizable.

Examples of monomers that can be polymerized or mis-polymerized are: Cf-olefins, aromatic vinyl compounds, such as s.B. Styrene, halogenated styrenes, (X-methylstyrenes, vinyltoluene and divinylbene sol, ot, £ - * msaturated Carboxylic acids, such as acrylic and methacrylic acid, and the Nitriles, amides and oils thereof, vinyl esters, vinyl ketones, Vinyl chloride, vinylidene chloride, l-vinyl compounds, such as e.B.

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Vinylcarbazole and Viiylpyrrolidon _f unsaturated Dicarboneäuran as s "B" PumaJ acid and maleic acid and the esters and amides thereof ι ovie dienes ,. Andei'e brauahbare monomers aridere Farl are, for "B, sweeteners containing olefinic groups, and compounds derived from phenols Ejind ixad aromatic compounds and Grüben en dlls one or more wasGerlöBliehmachendi Gz'uppen contain Bexcpiele of such compounds bind AJ cryloylaminoberiKoeuäure, N-Acrjdoylanlin-5 "" or "4-au! Fonsäure, AcT'yloyla.xiinonaphtholöulfon'-eäureaund Pentadienoj laininonaphthulBUlfonsaurenoPalymerisable fionomers of these types can be added in the dye bath or in the printing paste together with the dyes or other ingredients.

The invention is explained in more detail in the following examples. The examples e are not in a limiting sense * All parts oind expressed in weight

example 1

0.03 parts dea dea Natriunsalzes dye t-Methacrylaylamino '?''(3' methacryl oylaffiitiophenyIbzo) -8-naphthol "= ^ ₁ 6 <= d ~ _ff eulfonoäure the top diazotized by coupling © ylaminoeE.ilia with 1-Kethacryloylaßiino = ö <=. siaphthp

sulfonic acid under achwr.eh acidic to weakly alkaline loading dlngoi ^ s * erhaltsr wrden _s "ad 0 ^ 15 parts Ammonivnnaeetat% iarden ia is aufgelöst- 150 TeiieEi iJasser, ^c -. parts of a duroli> näßtes Wollsergetexts.lstoffs be in DA® - Wäirhe ^ ml ^ r-rgeführt nmd -gerührt ^jb: .s the temperature Ί 00 ^a 0 ez ^^ calibrates has ο the Eärbebad is cooked 30 minutes u xi <? then go to 7C ⁰ C

QQ 9 8 3 67 2 0 2 1 ^{ßAD 0R! GINAI} -

cooled, during which zi 0.075 part of sodium metabioule; and 0.075 part of ammonium sulfate can be dissolved.

The temperature is increased again to 100 G and the treatment is carried out for 20 minutes at 100 ° G. Finally, the fabric is removed, rinsed and dried *, It is dyed in a bluish-red shade, which has a very good fastness he has the I ₀ S ₀ O ₀ Wash Test No ₀ 3. The fastness to natural treatment and to solvent extraction is better than that of a similar dye to which no sodium metabisulphite and no ammonium per sulphite have been added _{or the like}

Example 2

100 parts of a Wolltextiletoffs be colored 60 minutes at 100 G in a solution of ⁰ '> part of beech rubbed ones in Example 1 dye, 3 parts of concentrated sulfuric acid and 5 parts of anhydrous sodium sulfate in 3000 parts of water

The dye bath is darn cooled to 70 ⁰ G, and 1 part Hatriummetabißulfit is eeetzt to ^ what 3I, the addition of 1 part ABjmoniumpersulfat connects> Temperature dsa bath is raised to 100 C, and the treatment is continued for 20 minutes at 100 ⁰ C the wool fabric is ontnon) men _rinsed uad dried

A reddish ldaua color is obtained, which is better Authenticity towards Wf.schon and sweating has one similar coloring, in which the NatriuBanetäbisulfit and the

009836/2021 BM>

Amnionium persulfate has been omitted Bind »

Instead of the quantities of sodium metabisulphite and iunmonitmipersulphate, used in the example above, 1.5 parts of these reagents can also be used.

Instead of adding sodium metabisulphite and ammonium persulphate Sum dye bath can 1 part of a 20 jSlgen (volume), 'sfaesoratoffperoxvds and 0.8 part of thiourea is added to obtain a reddish color with good braiding.

Instead of adding sodium tetra sulfite / ammonium persulfate or thiourea / sulfate peroxide to the replenished dyebaths, the dyed woolen textile can be removed from the exhausted dyebath, rinsed if necessary and then placed in a fresh bath containing 3,000 parts of water and sulfate sulfite / sulfate sulfate / sulfate sulfide with the amounts of sodium metabisulfite given above or contains thiourea / hydrogen peroxide. The fresh lad is then two. Boiling heat ^ and the treatment is 20 minutes fortgesetat _e The fabric is then removed ₈ gespi-Ht and dried "There are Pürbun obtain ^ s" which have similar iJchtlieit as if dis reagents are added to the exhausted Farbebaul "

Example % ■

0.03 part of the matrix salt of the dye .2-iletliacryloyl ~ amino «? - (3 ^s -msthacryi oylaminopheiiylaso} -8-naphthoic acid (produced by coupling dlazotiex-iem

009 836/2021

^bath

oylaminoanilin with 2 * £ ilethacryloylaiaino- naphthol-6-sulfonic ~ Bfiure under echwach alkaliechen conditions) and O _t 15 parts of ammonium acetate will ι dissolved in 150 parts Waeeer ,, 5 parts of a bulked Ky .on-GG-fabric (commercially available as
"Banlon * known) or 5 parts of nylon-6 fabrics
are introduced into this Filriebad and stirred, during which the temperature of the bath at 100 ⁰ C increases wirdc The
Dee temperature bath FIRD 30 minutes 100 ⁰ G held, and the dyeing bath is c m & ercchöpftc by adding 0.15 P art to Essigeäure Des Färbobad 10 Hinuten gelto ^ ht and then cooled to 70 ⁰ C,

0.075 parts and 0.075 parts Hatriunimitabisulfit Aismonlunipersulfat verd.en zuges®; st _e oils Temperatxir Mrbsbade dee "is erhöhtj to 100 C and the Behaedliiag, in this Teiape temperature ~ 20 minutes from ^ eführts The Testilnt-off is removed dean, geepült and, dried"

A gcharlaa red color is obtained, which is better Fastness to wet treatments is all similar® Coloring which has been obtained from a treatment,

at öar dae Kfetriionetoldsulfit vmä ά && has been slEä «

Angt®lle der M © agta d ©echs fets'ii ^ ügtabisttlfits- uod

p © ^ 3wlfsrfes ,. the Ib oMgca example was adorned with B ₈ kötmen

0 _D 07 £ ei3c; M © tE4t3s & © S <sbis * ai £ It iwÄ O ₉ 05 parts

sulfate

Äasteile

Q 0 S 8 3 8/2 often ^SSAD

For the exhausted dye bath, the dyed nylon textile can be removed from the exhausted dye bath, rinsed if necessary and then placed in a fresh bath which contains 150 parts of water and the amounts of sodium metabieulfite / asmionite persulfate specified above. The fresh bath is then heated to the boil and the Treatment is continued for 20 minutes. The fabric is then removed, rinsed and dried. Dyeings obtained with a similar fastness as those in which the reagents were added to the exhausted dye bath _e

Example 4

0.03 part of the sodium salt of the dye 2 ~ Methacryl ojlamino « 6- (5 '-methacryl oylaäd.no-2 · -sulf ophenylazo) -5 ° -naphthol »7 ° = sulfonic acid (prepared by coupling diazotized 5-methacryloylaminoaiiline-2-sulfonic acid with 2-MGthacryloylamino-5-naphthol-7-sulfonic acid at pH 8 to 9) »3 parts of urea and 0.067 parts of the condensation product from nonylphenol with 8 moles of Äthylenoxyc. are dissolved in 30 parts of water An unmercerieiei-tos cotton cloth is made through this solution padded, squeezed to remove excess fluid au, and then dried

The cloth is again bubbled through a solution of 0.133 parts of 4,4 '~ ~ Aaobis (4-cyanopentanoic acid) _e which is dissolved in 30 parts of acetone, padded, the cloth is dried, steamed for 10 minutes at 102 ⁰ C and then 10 minutes at 100 ^{Washed at 0} C in water, which contains 2 parts of a synthetic detergent ie 1000 parts of water »

009836/2021

It is dyed in an orange shade, which has an excellent fastness to washing sharp "If the 4,4'-azobis (4-cyanopentanoic acid) is omitted from the second Klotzflüesigkeit, then only one of the dye occurs vernachläesigbare Fixage a ₀

According to another variation of the process, 0.03 parts of the dye, 3 parts of urea and 0.1 part of a 5% (weight / volume) solution of di-t-butyldiperphthalate in acetone are added to 30 parts of water padded through this liquid, ^v squeezed ond, in order to separate excess liquid. The textile fabric is then dried at 50 ° C. and then ^{steamed for 10 minutes at 102 °} C. »Sr is then washed in a solution of 2 parts of a nonionic detergent in 1000 parts of water for 10 hours at 100 ° C. * An orange hue is obtained which is beßltzto If the di ~ t-butyldiperpt, terephthalate omitted a very good JSehtheit to washing liquid from the block, then only a very small Fixage enters the dyestuff is an _o

The dye can also be obtained by printing according to the following Have a prescription applied?

0.5 parts of dye are dissolved in 19 parts of water, and the solution is stirred into 19 parts of emulsion thickener, together with 12 parts of a 9 # solution of dee Thickener "Indalca PA / 3 * ο 0.5 Tt-ile ammonium sulfate be stirred in until they are dissolved, and then 0.1 Part J) i-t-butyldiperphthalate stirred in »

009836/2021

The printing paste thus prepared is applied to bulked nylon 66 fabric ( "Banlon"), and the fabric is dried in an air stream at 40 ⁰ G The dried oppression is steamed 30 minutes at 102 ° C and then rinsed for 10 minutes at 60 ⁰ C washed in a Lööung of 2 parts of a nonionic DETERGENTES in 1000 parts of water * It is finally rinsed and dried.

Ea an orange-colored imprint is obtained _f which has very good fastness to washing

In the following table Bind further examples of dyes given according to the invention, which are obtained when _s diazotising the amines listed in the second column and kuppeltr to those given in the third column components

The fourth column of the table shows the hue obtained when the dye is applied to the textile materials given in the fifth column by the methods described in the examples given in the next column _{or the like}

009836/2021

O O OD OO CO

5 3-methacryloylaoinoaniline 1 -Methacryloylaaino-e-naphthol-
4 * 6-dieulfoic acid practically
Red Wool
Βαααν · 2
4th 6th Anllin-3-Bulfon-4 '- (methmcryloyl-
amino) -anA144 1 -Hethaoryloylamino-8-naphthol-
3 , 6-disulfonic acid bluish-
Red Voile
Bauaswo 2
4th 7th Aniline ^ -euliOn-fl-fliethacryl oy 1-
aminoethylamide 2-methaoΓyloylamino-5-naphthol-
7-BvO.fonal acid peculiar-
orange HyI on
Wool 3
2 C. 3 ~ (3 "15 ■" -Blsoietliacryloylamlno-
benaoy lamlno) -arilllii 1 -acetylamino-e-soaphthol ^, 6-
diöulfonaäuro RuMn Wool 2 "1 2'raphthel »8-sulfenic acid orange * yl ση 10 O 1 - ^ Naphthol -3 »8-di.eulf oneäwr · orange Wool 2 4- (4 ' -Methyl »?% 5" -BiemethaciYloyl-
i-Tninobenzolsxilfosiy (amino) aniline 2-Aoβtyla! Bino-5-naphwhol-7-
ßulioneäuro reddish-
orange nylon 3 * ■ · ti 5 -Naphthol — i-eviIi'ottsäOrtj orange KyI on 3 13th Il 2-Kaphthol-6 ₁ β-dleulfonic acid orange Wool 2 U Aniiin ^ '- snliOn'-di-Cfl-methacryloyl-
oxyethyl) amide 1-acetylamino-e-naphthol-3 _f 6-
sulfonic acid bluish'·
Red Wool
Bauinwo 2
4th 15th It 2-kaphthol-7'-9ulx'cnaic acid orange KyI on 3 16 Aniline-2-sulfone-di- (fl-methaoryloyl-
onlnoethyl} amide 2-Ac θtylasdno-5-naphthol-7-
bvH fonsäure orange HyI on 3 17th η 2 "Aeetylamlno-8 'Rephthol-6-
sulfonic acid echarlach HyI on
Wool 3
2 18th V • -Naphthol-3 »6-diaalfonaic acid orange Wool 2 iy 2-amino-3 ³ $ 4 -blamethacryloylamino-
eiipheayleulfone 2 ~ acetylamino-5 ~ naphthol-7-
sulfonic acid orange nylon
Wool 3
2

CD (Jl CO

20th 2-A »lno-4 'Hatthyl-3 *, 5 ⁵ -biamethacryl- 2-aoetylamino ~ 8-naphthol-6- BOharlaoh .. HyI on 3 oylaminodiphenyl sulfone sulfonic acid Wool 2 21 η 2-Naphthol-7-SuIf one & ur β orange Wool 2 22nd It I-raphthol-3 , 8-dimilfonic acid orange Wool 2

CD CO CD CO OD

ro IF

O Ni

CO

co

cn co cn

Claims (1)

Patent claims: Process for dyeing fiber materials or polymers Filming, characterized in that one is the fibrous material or the polymeric film with a solution or suspension of a Monoazo dyes of the formula CO - C = CH ₀ -η - (SO _x H). treated, wherein A represents the residue of a diazo component of the benzene = -, naphthalene or stiltene series, B represents the residue of a naphthol coupling component coupling in the ortho position, j P represents a grouping of the formula -0-, -JiH- or -NHNH-, τ . represents a gaiusa number and π represents an integer with a value of at least 2, whereupon the treated material or the treated film is subjected to the action of a polymerization catalyst, 2c method according to claim 1, characterized in that m is 2 or 3 and; each of the groupings represented by P, -NH- iet _o 3tf method according to claim 1 or 2, characterized in that 009836/2021 BATH ORIGINAL net that ζ 1 or 2 iso 4ο method according to claim 1, characterized in that the dye the poimel N «N - E has, wherein the Mfcthacryloylaiainogruppe is bonded to the ring B in the m- or p-position to the azo group, the Hing B by chlorine or lower alkyl, lower alkoxy, sulfonic acid or sulfonamide groups can be further substituted and E represents the residue of a methacrylic cy! aminonaphtholsulfonic acid, 5 ο method according to claim 1, characterized in that the _$ Parbstoff the formula N = N-S Beeitsstj, in which the sulfur atom is bonded to the ring B in the o, m, or p-position to the azo group, the ring B further by chlorine or fluoroalkyl _? Lower alkoxy ,, sulfona acid or 009836/2021 ■ μ- Sulphonamide groups Buostituiert may be, 1 alkylene or Is phenylene and is the remainder of a methacryloy! Aminonaphtholsulfonic acid 60 The method according to claim 1, characterized in that the dye the fo / inol CH, CCQSH CH "= CI CC0H3 CH. CC05.Ü Qy. H - E • COMR beeitat, wherein the sulfonylamino or acylamino group to the Ring B is bound in the m- or ρ-position but Axograppe, the 009836/2021 ^BATH Ring B expanded by chlorine or lower alkyl, lower alkoxy, Sulfonic acid or sulfonamide groups can be substituted, R represents hydrogen or a lower alkyl group and E represents the residue of a naphtholevulfonic acid or an acylaminonaphthol acid, in which the acyl group is a methacryloyl or saturated acyl group is o 7c method according to claim 1, characterized in that the dye off the Pcrrael - P - CO - C a CH ₂ ) ₂ CH- beaitzt, in which the sulfur atom is bonded in the o-, ■ ·> or p-position to the azo group, X represents alkylene, P represents -0 · or -9H- and £ represents the residue of a haphtholsulfonic acid or an acylaminonaphtholsulfonic acid in which the acyl group a methacryloyl or saturated acyl group iat _o 8. The method according to claim 1, characterized in that the dye the fonael ORIGINAL BATHROOM 00 98 36/2021. 2 - t beeitit, in which t 1 or 2 let, the methaoryloyl group or -groups is EiQg L in the a- or p-position sur sulfonyl group are bonded, the groups G- and L further by 'lower alkyl groups or ChIo: - can be substituted' and £ the remainder represents a haphtholsulfonic acid or an acyl aminonaphtholsulfonic acid, worir. the acyl group is a methacryloyl or saturated Aoy! group isto 9o method according to one of the preceding claims, characterized in that the amount of the catalyst used is in the range from 1 to 500 Qew .- ^, based on the Qewioht of the Parbetoff% is fO * Ttrfahrea according to one of "the preceding claims, since" by gokennaeichnet that a dye that is no more than Contains kwei sulfonsaur groups, on din wool or a synthetic «polyamide? axil * aterial is applied by a paint process» If ₀ method according to claim 10, characterized in that the dye has only one sulfonic acid group " 009836/2021