DE2444522C3 - Alkoxylated dyes containing at least one water-solubilizing group which can be split off under dyeing conditions - Google Patents

Description

F - / - N -CM, O -Z \ (lh |

correspond, where means:

F the remainder of a dispersion or l'ig-

ment dye.

-X ₁ -N-- a terminal or in Moieküi ^! built-in acid amide resol.
R.

X ₁ the divalent bridge CO. -CS-, C ~ NH or SO,
or a carbon atom which is part of a nitrogen heterocycle and is adjacent to the ring nitrogen.
R is hydrogen or a C _{1 -C 4} -alkyl radical. possibly by Malogen. Cyano, hydroxyl or C, -C ₄ -alkoxy is substituted. or —CM, OZ means, or
R together with

X,

also a Stiekstoffhelerorint :.
X, CO or SO,.
R _{1 is} an alkyl radical optionally substituted by cyano or hydroxyl and having a maximum of 5 carbon atoms or a phenyl or benzyl radical. for example by alkyl having 1 to 4 carbon atoms. Alkoxy of 1 to 4 carbon atoms. Halogen. Hydroxyl. Amino or nitro groups can be ring substituted and or a hydrocarbon residue bonded _{to X 2 via an oxygen atom or an amino group and}

Z is unsubstituted or substituted by alkyl having 1 to 3 carbon atoms. Phenyl or olycidyloxy substituted mono-polyalkylene glycol radical with an average molecular weight of at most 2500 and 2 to 4 carbon atoms per alkyl unit. the hydroxyl groups of which can be formed with an alcohol with a maximum of 4 carbon atoms.

M ₁ mean I to Λ uikI / i, I to '.

2. Process for the preparation of the alkoxylated dyes according to Claim I. characterized in that that he

F -

CH, () H

or

OH

X, R ₁

(3h)

wherein F, Xi, R, n \, X ,, Ri and n _{2 have} the meaning given in claim 1, with
b) an unsubstituted or substituted alkylene oxide in the presence of a metal alcoholate of a transition metal of groups IV, V or VI of the periodic table and optionally an alkali metal hydroxide or an alkali metal alcoholate of an alkanol having 1 to 4 carbon atoms
implements.

3. The method according to claim 2, characterized in that one alkylene oxides of the formula

ClI,

CU R,

in which R _{7 is} hydrogen, Ci - Ci-Alkylrcst. Phenyl radical or a

CfI, --CM, O remainder

means used.

4. The method according to any one of claims 2 and 3, characterized in that the reaction in Presence of a metal alcoholate of the formula

Me (O-AkMR _n ) ,, _r

wherein Me is a ς-valent transition metal dei groups IV, V or VI of the periodic table, Ak Ci-O-alkyl, halogen-C2-C ₄ -alkyl, phenyl, benzyl or cycloalkyl with a maximum of 12 ring carbon atoms, R «halogen orC _t - Q-alkoxy, rl bi; q and q means A, 5 or 6.

The present invention relates to water soluble ones alkoxyated dyes of the general formula (la <o or (Ib)

F f X, N CM, O Z

mler

1 (N (W. O /

I x _: κ, '

correspond, where means:

Ha)

HhI

I 'the remainder of a dispersion or Pignientfarhsioffes,

-X ₁ -N a terminal or an acid aniide residue built into the molecule,
R.

X, the divalent bridge —CO—, —CS-, C = NH or —SO, or a carbon atom that is part of a nitrogen heterocycle and is adjacent to the ring nitrogen,

R is hydrogen or a C ₁ -C ₄ -alkyl radical which is optionally substituted by halogen, cyano, hydroxyl or C ₁ -C _{4 -alkoxy, or is —CH 2} —O — Z, or

R together with

-NX ₁

or an alkyl radical with 1 to 4 carbon atoms, which is optionally substituted with halogen, cyano, hydroxyl or alkoxy having 1 to 4 carbon atoms can be. The substituent R can also be part of a nitrogen hetero ring in which the Groupings

- CO -,

- it -

and

C = NH

also a stickstoiTheterorinu,

X ₂ CO or —SO, -,

R, an alkyl radical optionally substituted by cyano or hydroxyl with a maximum of 5 carbon atoms or a phenyl or benzyl radical, for example by alkyl having 1 to 4 carbon atoms. Alkoxy of 1 to 4 carbon atoms. Halogen, hydroxyl, amino or nitro groups can be ring-substituted, and / or a hydrocarbon bonded _{to X 2 via an oxygen atom or an amino group.} Scraps of fabric and

Z is unsubstituted by alkyl mono- or polyalkylcnglycol radical substituted with 1 to 3 carbon atoms, phenyl or glycidyloxy with an average molecular weight of at most 2500 and 2 to 4 carbon atoms per alkylene unit, their terminal hydroxyl groups with an alkanol with a maximum of 4 carbon atoms may be ethereal,

Ji ₁ I to 6 and

ii _{2 means} 1 to 3.

The radical Z is advantageously derived from mono- or polyalkylene glycols, which are generally 1 to 40 Alkyleneoxy groups, preferably 5 to 30 alkyleneoxy groups, and 2 to 4, preferably 2, per alkylene unit or have 3 carbon atoms. Polyalkylene glycols, including dialkylene glycols, are sn preferred over the monoalkylene glycols.

The radical Z is bonded to the methylene group via one of its oxygen atoms. Is the alkylene glycol residue substituted, it can be on individual alkyleneoxy groups, preferably on ethyleneoxy groups, phenyl, s.s. Have alkyl with 1 to 3 carbon atoms or glycidyloxy radicals.

These alkylene glycol radicals can also be terminated with an alkanol having a maximum of 4 carbon atoms be ethereal, e.g. B. with n-butanol, n-propanol, ethanol f> o or especially methanol. However, the unsaturated products are preferred. The residues Z are derived z. B. of ethylene glycol, diethylene glycol, optionally substituted by methyl, phenyl or glycidyloxy Polyethylene glycols, 1,3-propylene glycol, 1,2-propylene- '· < glycol, polypropylene glycol, polybutylene glycol, polypropylene polyethylene glycol.

In formula (Ia), R preferably denotes hydrogen may be included, as in derivatives of the 1-unsubstituted 5-pyrazolone or 5-aminopyrazole or the barbituric acid or cyanuric acid, such as. B. 2,4,6-triamino-substituted or 4-hydroxy-2,6-dia.nino-substituted Pyrimidine or triazine derivatives or their ethers. If desired, R can also be a second grouping - CH2 - O - Z represent.

Depending on the type of starting components used to prepare the dyes according to the invention can grouping the formula

or

-X ₁ -N-CH ₂ -OZ (2a)

- Ν —νΉ, —O —Z (2b)

X ₂ -R ₁

be connected to the dye molecule F directly or via any bridge members. As bridges come z. B. divalent hydrocarbon radicals,

ΐτ, for example, lower straight-chain or branched ones Alkylene radicals such as methylene, 1,2-ethylene or 2,2-propylene group, the 1,1-cyclohexylene group or lower alkylene radicals, such as the vinylene group, also ether groups, thioether groups, aminoalkylene groups or

V> amidoalkylene groups, as well as unsubsti; ; ated or substituted imino groups which can form methylolatable ureido, thioureideo or gauanidine groups.

The water-soluble, alkoxylated according to the invention

-I «. th dyes of the formulas (Ia) and (Ib) are produced by

a) a methylol derivative of the general formula

FfX, -N-CH ₂ OH \ (3a)

ι
R.

oJer

τ:

FTN-CH ₅ -OH

X ₂ R ₁

(3b)

wherein F, Xi, R. n \, X>, Ri and n _{2 have} the meaning given, with

b) an unsubstituted or substituted alkylene oxide in the presence of a metal alcoholate of a transition metal of groups IV, V or Vl des Periodic table and optionally an alkali metal hydroxide or aluminum metal alcoholate Alkanols with 1 to 4 carbon atoms

implements.

If the amide nitrogen contains a second -CHjOH, so this methylol group can also be etherified according to the invention.

It is particularly advantageous to start from dyes which have at least one N-methylolated Have carboxamide or sulfonic acid amide group.

The N-methylolated dyes used as starting components are produced by reacting corresponding dyes which contain at least one acid amide group which can be methylolated with formaldehyde or a formaldehyde-releasing compound. Suitable formaldehyde donors are, for. B. trioxane, hexamethylenetetraamine, but preferably paraformaldehyde. The reaction of the amido-containing dyes with formaldehyde or formaldehyde-yielding agents is generally carried out in an aqueous or aqueous-organic, but preferably in organic medium at temperatures of 40 to 10O ⁰ C.

The disperse or pigment dyes, in the after the present process at least one non-ionic water-solubilizing grouping. ^ is introduced can belong to the most varied of classes. These are, for example, optionally metal-containing mono- or polyazo dyes, including Formazan dyes include azomethine, methine, anthraquinone dyes and their substitution products and condensation products, naphthoperinone, styryl, azine, thiazine, oxazine, dioxazine, indigo, Indanthrene, quinophthalone, acridine, acridone, thiazole, Xanthene, nitro and nitroso dyes, triphenylmethane dyes and polycyclic higher condensation Dye systems from the series of benzanthrones and dibenzanthrones and their condensation products. Among the azaporphin dyes, the phthalocyanine dyes have, because of their comparatively easy accessibility preferred interest. These can be used both as metal-free compounds and with complex-bound metals z. B. as cobalt, copper and Nic'.elphthalocyanine, use. Further pigment dyes from the isoindolinone series are also suitable for the process according to the invention.

Among these dye classes are the disperse dyes in the series of metal-free azo and Anthraquinone dyes and the pigment dyes in the series of copper phthalocyanine, azo, especially Disazo and acridone dyes preferred. These dyes and pigments should advantageously at least Contain 3, preferably 4 to 6, aromatic rings per molecule.

In addition to the acid amide group required to introduce the non-organic hydrophilic groups according to the definition, the dyes mentioned can be further substituted in the usual way. As another Substituents come into consideration, for example: hydroxyl, cyano, nitro, halogen such as fluorine, chlorine or Bromine, unbranched or branched, optionally substituted alkyl groups such as methyl, ethyl, isopropyl, Amyl, cyanoethyl, trifluoromethyl, chloroethyl and alkoxyalkyl groups, cycloalkyl groups such as cyclohexyl and methylcyclohexyl groups, aryl groups such as phenyl and toluene groups, aralkyl groups such as benzyl or phenethyl groups, ether groups, e.g. alkoxy, such as methoxy, ethoxy or phenoxy or benzyloxy groups, Amino, alkylamino. Aralkylamines), arylamino, Acylamino, such as the acetylamino and benzoylamino groups. given: If N, N-clisnstyled carboxylic acid and sulfonic acid amide groups, acyl groups, such as lower alkanoyl, aroyl, alkoxycarbonyl, alkylsulfonyl or arylsulphonyl groups, sulforic acid alkyl or aryl ester groups. Any in these substituents Aromatic rings that are present can in turn be substituted in the same way.

Particularly preferred dyes which have at least one to introduce the nonionic according to the definition have hydrophilic group required acid amide group, derive z. B. of the following Connection classes from:

a) monoazo dyes of the formula

D-N = N-Ar-N

(B) ₂ _ "(4)

in which D is the radical of a diazo component, especially of the benzene series, Ar is an arylene radical, especially an optionally substituted 1,4-phenylene radical, R ₂ and R3 are each an optionally substituted alkyl group and B is the radical of a coupling component ζ. Β. of phenol, acylacetic acid amides, 5-pyrazolones, 5-aminopyrazoles or hydroxypyridones and a is 1 or 2, where at least one of the radicals D, Ar, E, P,., and R3 is an acid amide group of the formula

-X ₁ -NH

i
R.

contains, where Xi and R have the meaning given have contains.

These azo dyes include those containing only one acid amide group capable of methylolation Dyes of the formulas (5) to (II):

N = - N - Ar - N

where Pu denotes an optionally substituted alkyl or aryl radical and Q denotes the group -CONH-, -SO ₂ NH-, -NH-CO- or -NH-SO ₂ - and the ring A can contain other non-water-solubilizing groups, for example cyano, Nitro, halogen, alkoxy of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms. Ar, R ₂ and R> have the meanings given above;

N - G Q- <f A > -

N — Ar — N (6)

where R / and P 'mean alkyl radicals which may contain non-water-solubilizing groups, and K ₁ ' can also be hydrogen and G can be

optionally substituted Alkylenresl represents. Λ, (), Ar. R .. and R ₍ h.-ibcn the meaning given;

R, U

17 |

NNH ₁

worm Bi a remainder of the coupling component of the phenol, Fnol, z. B. Acylessigsaurearylamidc ·. l'yra / o ι lon-, aminopyra / ol- or I hydroxypyridone series represents. A. () and Ri have the meaning given;

Phenoxy. l'hcnylthio or Alkoxycarboiivl with more than ¹ J carbon atoms:

I)

B,

HIl

where D has the meaning given and B. denotes the radical of a methylatable N-heterocyclic coupling component, for example a radical of barbituric acids. 2,4,6-trisubstiluierten pyrimidine compounds, especially 2,4,6-aminopyrimidine compounds, 6-1 hydroxy pyridones, 3,5-dioxopyrazolidines or 4-llydroxy-2-quinolones, which can contain the above-listed substituents customary in azo dyes;
b) disazo dyes of the formula

N (I

NNH ₁

(S |

ν »urine rush S \ iii'nc> ic ciie a

ie nedeiiiuiiu h.incii.

IN

Ar

R,

(i,

Χ, N11,

wherein (ii is an optionally by heteroatoms, especially oxygen atoms, interrupted alkylene types bedeulel and D. Ar. R and Xj the given -, Have meaning;

R-

1) N N

¹ R,

Ml X, R ,,

wherein D. R :. R ·. Ri. X.> the meaning given above., have and I. hydrogen. Halogen. /.B. Chlorine. Alkyl groups with the highest ■? Carbon atoms. Alkox ;. groups only have a maximum of 4 carbon atoms.

Wed

CII C (I ^v .! I
(o (I].

where Rt represents arylene radicals, especially optionally halogen, alkyl or alkoxy-substituted phenylene radicals, and An, Ar _; and R have the meaning given.

d) Disazo dyes (pigments) of the formula

CONH "i, Ml (i)

I) N N ■ A -N N

Ar N

R,

R,

IBi,

in D, A. B, Ar. R.>. Ri and a have the meaning given and where at least one of the radicals D, Ar, B, Ri and Ri is an acid amide group of the formula

X ₁

NH

wherein Xi .i.id R have the meaning given contains.
c) Disazo dyes (pigments) of the formula

CO-Ar ₁ N NH, NN Ar, CO f 13 »

NH R ₅ Nil R ₅

wherein B _{3 is} the remainder of a coupling component containing two enolizable ketomethylene groups. Ar, and Ar ₂ an arylrc-st and Rs an optionally substituted arylresi. especially of the benzene series.

These disazo pigment dyes include, in particular, compounds of the formula

MICOCH N
(OCH,

N Ai ₂ (O
NH

men or halogen substituted arylene radical. especially the benzene series, such as. B. a phenylene or diphenylene radical, mean
d) Anthraquinone dyes of the formula

Ya O Y ₁

1161

OH
\

worm T; and T _2, independently of one another, each represent a phenyl radical, which is represented, for example, by halogen, alkyl with '. up to 4 carbon atoms. Alkox ν with 1 to 4 KoniensioffatOiTien, Cyano. Nitro and alkylsulfonyl with 1 to 4 carbon atoms can be substituted and Tj one optionally by alkyl with 1 to 4 carbon atoms. Alkoxv with I to 4 carbon atoms-Y, O Y ₂

wherein E is halogen, especially bromine or chlorine, or alkyl or alkoxy, especially methyl or methoxy, m 1 or 2 and Yi, Y2, Y] and Yj are each hydrogen, an optionally substituted by an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical substituted amino or hydroxyl group or a nitro group, where one of the symbols Y-. Y ;. Yi or Y <or the

κι

The anthraquinone nucleus itself contains one to introduce the type of sulfonic acid amide. not; ionogenic water-solubilizing agents (inippiening Typical representatives of the abovementioned dye class

qualified Sänreamidgi lip, especially one (arbonsiiii sen are:

\) Μοηο, ι / οΙ, ιι tisloilc

λ, I I) lspCI SIlMlsi.ll | l-ill) | lc

(! 1 / ONII

N N

O, N

O, N

(M

N N

(, IL

NIK (HIi ₁

(N

(MU

N N

(Ml,

NII (OCH,

O, N

Cl

N N

NIIC (X II, OCII,

(MU

( WU

( II,

(λ, Ν

N N

NO,

/ NN

NIK (XII,

NKMI ₄ O (O

Nile CO

NO,

O ₂ N ■ '. · - NN

(H, ill, O CW, CiI, CN

Cl
CM, CH, O CH, (H, CN 40 "ο

H fin · ',,

MK (KIUII,

Oll

- CONH

N N

C ₂ H ₄ CN

OA

Nile. NIK OCII,

(, II.

OA

NN

, H ₁

NN

CH,

cn,

N N (C

oil

12th

i \ lli

ι \ 1111

ι IX ι

N (K

CN
(ONH,

Nile

CN
NNC (Nil

^(N
NIICH ₂ CII.OH

CII,
CN

CM"

lXIi

SOAH

oil

CO NH NNC ¹ H Vo

CO NH

, XIIlI

COCH,

_NH

N N CH

Π 14 y

ro [

II, (N N (Il (X \ ι

NO, ^{(() N11}

Nile,

<>:> · N N, .WH

Cl S (KNH,

OCH ₁
Cl NN (II (ONII ■ Cl lXYIIl

(II, ^{(<) (ll} <OC,

(II.
CN
^Π Ν -

NNCC _{S () 2N1 | 3} , XVIII,

OH

CH:

C N

N ·

^{N N (Γ}

SO ₂ NH,

SO ₂ NII, ^{() M}

X ₂ I pigment dyes
Cl

NN-

OH ^C1

lXXMl

(ONH -

OC H,

((XH,
₍ - _H OCH, (XXVIh

CONH · Cl

OCH,

15th

ocn,

K "

CH ₁ Cf) NII

N N

NN '':

SO.NII,

N N

I.
ό N N \ ( (Il ( (Il N V ₂ H ₄ C ( NII > οι / I disazo dyes N C ₂ II ₅ Disperse dyes ο \ 11. OCH ν ' CH ₂ ι
NN '( "> - NH ONH ₂ (II, N / NN <' π () Ό , / N N ·: "' () N (K (

(XXVIiI)

(XXlX)

(XXX)

(XXXI)

(XXXII) (XXXIIaI

^v s N

(WMIIi

IK) Il ο

17th

in) PigniL'nlf; irhsto (Tc 18

Cl

Cl

i)

N N CII CONII

CC) CH, NIICOCH NN
COCH.,

(XXXIV)

Cl Cl

Cl

N N

NO ₁

OH

Cl

f ' co

NH NN --C> Cl
TY ^ν ] NO ₃

CONH v

(XXXV)

C!

NHCO

Cl

NN CH CONII {'" ' ■ · ■,

COCH,

Cl NHCO -CH -N N

COCH,

Cl

co

Nile

(XXXVI)

CII,

Cl

Cl

co I Nile Λ /

J J

CII.,

NN CH CO Nile ■

COCIl, Cl

(XXXVII)

NIICOCH N N

CII, COC H,

CO

I.
NH

H, C

OH

N N ''

(H, OH

' ^: '> NIICO ^ '· NN (H,

Cl

CH,

(XXXVIII)

COOCII, CII.C COOCH, CH, Cl

19th

/ ■ /

C (JNH · ■ '· ■

NHCO

OH _{π α} HO

N Ν - f / '^ V- N - N

20th

(IXL)

Cl

Cl

Cl

C! CH.,

CO -NH <

N - Ν - CH-CONH

CO-CH.,

CONH

OH

CH,

NHCO -CH-N = - Ν— '■

! CO-CII,

Cl
Cl

S- NIICO

MO

N N

Cl

Cl

NN

; ·) Anthraquinone dyes O OH

Cl

(XLl

(XLI)

(L)

O HN - <> ■ NHCOCH ₂ CfI,

/ Χ,

O NH ₂ J ¹ / /
CH CII, ! I
χ * / ■ ■
'■ / I.
CONH ₂ CONII, I.
\
Y V CH, Il
O HN- < 0 NH ί

(Ll)

(LII)

O HN

21

O HNCO

, - A i f ϊ ί J

V-CONH O O

> —Π

Cl- /> -CONHO

O NH,

CONH,

Cr,

Cl

O NH

NH

/ V N N

Ii!

c c

■ /

N Ο C).

NH

HN

NH

22nd

(LlIl)

(I IV)

(I V)

ι LVI

■ CO — HN — O

-HN- C. /
C. C-
Ι; HN - O N NH, It
**! O

--NH- CO - ■;

(LVII)

CO NIl
O

N
Il

■■>) ΓΙιπικ- I aibslnlk iilV (SO, Nil CII, (Il (I I.,

Ml

SO.Nile

Il M ! YM

NO.

Nile

(O Nile

OH

NO, O CONII,

Il XXI

XXIh

Cl
(IC

Nile

(I C

(I.

Cl

Cl

U.N.

, XXIIIl

C i Cl

egg

Ik-: for the etherification according to the invention Alkylene oxides in question are preferably alkylene oxides of the formula

( H,

(I! R-

(I.

wherein R is hydrogen. Alkyl with I his! Carbon atoms. Phenyl or one

CH-

(H

means. Examples of such alkylene oxides are ethylene oxide. Propyler.oxyd. Styrene oxide or digly lidyl ether. Propylene oxide and, above all, ethylene oxide are preferred.

The reaction with the alkylene oxide is expedient in the presence of a metal alcoholate, carried out as a catalyst, which is preferably of the formula

Me (O AkuRj,., .. (IXi

ViIYiI: Me a "-few transition metal from the group iV. '■ <or Vi of the periodic table. Ak phenyl. Benzyl. Cycloalkyl mil at most 12, in particular 5 to 12 before aiieT, i to 12 Ringkohienstoffatomen. Halogenaikyi with 2 b: s "carbon atoms or, preferably, alkyl with 1 to ^d carbon atoms. R-. Halogen or alkoxy with up to 4 carbon atoms, r ! To q and q 4. 5 or 6 meaning. Bromine or preferably chlorine

At this. Chemical alcoholates are in particular alcoholates of transition metals, groups IV, V or VI of the 4th, 5th or 6th period of the periodic table according to the Langes Handbook of Chemistry. 10. AufL 1967, pages 60 and 61. These transition metals, including elements of the intermediate groups, groups a or groups b genanni include titanium, zirconium, hafnium, vanadium, niot tantalum, chromium, molybdenum and tungsten. When Res -O-Ak is preferably a radical of an alkanol, such as. B. methanol, ethanol, /? - chlorine ethanol, isopropanol, n-propanol, n-butanol, sec- ode tert-butanol, or also phenol, benzyl alcohol or a cycloalkanol with advantageously 5 to i: carbon atoms, such as cyclododecanol . As alkoxy, R _{8 is} usually different from -O-Ak and can be ζ. Ε methoxy, ethoxy, propoxy or preferably ten butoxy. The reaction with the alkylene oxide in the presence of metal alcohols of the formula is preferred

Me ₁ (O --Ak,

worm Me ₁ zircon ^{! V} , niobium'-. Aunt! ^v , tungsten ^V! or Moiybdän ^{V |} , Aki alkyl with 1 to 4 carbon atoms or Haiogenaikyi with 2 to 4 carbon atoms and ι 4. 5 or 6 according to the valence of the metal, carried out. Particularly suitable metal alcoholates correspond to the formula

Me ₂ IO-Ak ₁ I ^ 120)

where Mei zircon ^lv . NiobV means tantalum ^v or tungsten ¹ · 'un < q, 4.5 or 6 according to the valence of the metal and Ak <has the meaning given.

The reaction mil the alkylene oxide is preferably carried out in the presence chics additional catalyst, namely in the presence of an alkali metal hydroxide or alkali metal alcoholate with an alkanol having 1 _bi:; 4 carbon atoms. Examples of such catalysts are lithium, sodium, potassium, rubidium or cesium hydroxide or the corresponding alkali alcoholates, as indicated for the alcoholates of the transition metals

The preferred additional catalyst is sodium or potassium hydroxide or a sodium or potassium alcoholate of an alkanol having 1 to 4 carbon atoms is used.

The metal alcoholates alone or together with ilen alkali metal hydroxides or alcoholates are advantageously used in amounts of 0.05 to 5%, preferably 0.1 to 2% or in particular 0.4 to ¹¹ %, based on the weight of the reaction mixture.

are used, the weight ratio of transition metal alcohol to alkali hydroxide is or alcoholate usually 9: I to I: 9, preferably 4: I to I: 4 or above all 7. J until 3: 7.

Suitable examples of transition metal alcoholates are;

l: i (O (H ₁ I ₅ (21.1 I TiilOC ,! Ul, (21.21 TiI (O CH (CH, 1.1, (2l.il Ia (OC ^- (CH,),!, (21.41 Ti / O · - " λ (21.51 Nb (OCH,), (21.61 Nb (OC ₂ H,), 121 7) Nb (O -CH (CH.,),), 121.X) NbIi) C (CH ₁ I ₁ I, (21.9) No / O Λ (21.10) WEEK ₁ ) ,, 121.111 W (OC (CH ₁ ),! ,, (21.121 Hf (O CH (CH ₁ I ₂ I ₄ (21.Ii) Hf (O- C (CH,)., | ₄ (21.14) Mo (O CH (CH,!,! ,, (21.15) Mo (OC (CH ₁ I ₁ I ,, 121.16) Ti (OC ₂ H ₅ I ₄ 121.17) Ti (OC (CH ₁ I ₁ I ₄ 121.IXI Zr (OC ₂ H ₅ U (21.19) Zr (OC (CH ₁ I ₁ I ₄ (21.20) Ta (OCH ₁ ) Cl ₄ (2! .2Ii Nb (OCH ₃ I ₄ CI (21.22) Ti (OC ₄ H ₉ I ₄ (21.23) Zr (OCH ₂ CH ₂ Cl ₄ (21:24) Ta! OCH ₃ )! OC (CH ₃ ),) ₄ (21.25) Zr (OCH ₁ ) CI ₁ (21.26)

IK
■■ nid: ! -. pick tin MkitlmH'tallliulrowde and - , -! ", Lukewarm LiOlI (22.1 ι NiiOH 122.21 KOII 122.3) LiO 'II, (22 4 | NaOC II, 122.5) N.i OC, I L (22 Μ NiIOC (CH ₁ I ₁ C2.7I K (HII, (22 X | KOCJU 122.9 ι KOCiCH ₁ I, (22.K) I. in the
Λ || / ι, |
...... general will be the implementation
Αη ,, νυ, Ι lw »; fpmnpra tiirpn in the Rprpiph with the
\ jr> n 10 hi «

160 "C, preferably 40 to 120 ° C. Carried out. Dk The reaction can be carried out at atmospheric pressure or at elevated pressure. Preferably amount the pressure I to 20 atmospheres or in particular I to 11 atmospheres. Ir usually with the so-called autogenous printing, i. h that by the reaction mixture at the given Temperature self-generated pressure, worked.

Depending on the intended use of the conversion products, 1 to 50, preferably 5 to 3 ( Moles of alkylene oxide attached to the dye.

It may be useful to carry out the alkoxylation in the presence of a second alkyleneoxy to carry out that which does not take part in the actual implementation. For example, mar react with ethylene oxide and propylene oxide or dioxane as a reaction medium or as a slurry medium use.

The reaction with the alkylene oxide has the advantage that under mild conditions, d. H. at deeper Temperatures and with a practically neutral Kaialysatorsystem alkylene oxides directly to an N-met can attach hylolierte dye compound. N-methylol compounds are already known in the schwacl Acid medium unstable, and in a strongly alkaline medium they form polycondensates or splitters Formaldehyde and water.

After the reaction has ended, it is advisable to: neutralize the reaction product with a base These are mainly alkanolamines such as monoethanolamine, diethanolamine or, in particular, trietha nolamine into consideration.

The new dyes are suitable for dyeing voi organic materials of various kinds, for example for coloring paints, oils. Grow Paper, leather and furs, but preferably for dyeing and printing organic fiber materials! especially textiles. Natural and synthetic fibers can be used as textile fiber material As natural fibers are z. B. named:

Cotton, flax, jute. Wool or silk
and regenerated as synthetic fibers
Cellulose such as viscose,
Cellulose ester fibers, such as
Cellulose-2 '/ 2- and Cellulosetriacel.
Polyamide fibers, e.g. B. such from
Poly-2-caprolactam (polyamide 6).
Polyhexamethyl-i-diamine adipate

(Polyamide b, b).

Poly-ft> -amino-undecansiiuie (polyamide 7),
I'olyurcihan- or polyolefin-, /. 15th
Polypropylene fibers,
linear polyester fibers, such as
Polyethylene glycol crephthalate or
Poly (M-eyclolirKan-dimethylol-ierephthalate fibers.
Polyacrylonitrile! ' isern oiler

acid modified polyester or ι

Polyamide fibers.

However, it is preferably a textile material made of cotton or, above all, of linear polyester fibers, in particular made of polyethylene glycol terephthalate, or ^ synthetic polyamide fibers.

These fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. 13. Mixtures made of polyaeryl nitrile / polyester, polyamide / polyester. PoIypstpr / Visrosp ΡηΙνρςΙΡΓ / ΥνηΙΙρ iinrl we: tllpm PnkpUpr / Cotton can be used.

The fiber material can be present in a wide variety of processing stages, e.g. B. in the form of Flakes, sliver, yarn, textured threads, fabrics. Knitted, fiber fleece or textile floor coverings,. ·. such as needle felt carpets, pile carpets or yarn sheets.

The amounts in which the dyes are in the. Dye baths can be used depending on the desired color depth vary within wide limits. In general, amounts of 0.1 to IO have been found Percentage by weight, based on the material to be dyed, of one or more dyes has been found to be advantageous.

The staining can be done in open or closed systems, e.g. B. Circulation equipment: <such as package or tree dyeing equipment, reel skids, nozzle or drum dyeing machines, paddles or jiggers. The material is treated advantageously in a remaining constant throughout the dyeing process volume in loose form or applied to _t mechanical devices.

Depending on the type of dye used, the fiber material is dyed in an acidic, neutral to slightly alkaline bath, but expediently at a pH of 3 to 7 and preferably 3.5 to 6. γ. The desired pH value of the dyebath is set or maintained by adding conventional pH-influencing agents. Such agents are, for example, inorganic acids such as sulfuric acid. Phosphoric acid, or organic acids such as formic acid, acetic acid and their salts, also weak bases such as hexamethylenetetramine, or basic salts such as alkali metal acetates, citrates, carbonates, bicarbonates and phosphates. Appropriately, buffer mixtures are used as pH-influencing agents, e.g. B. Mixtures of primary and secondary alkali metal phosphates or ammonium acetate or a mixture of sodium acetate and acetic acid.

In addition, the bathroom can use other tools commonly used in the textile industry, e.g. B. network, restraint, carrier or (o Contain leveling agents, for example neutral salts such as sodium sulfate or ammonium acetate or - each according to the type of dye used - particularly non-ionic and cation-active, possibly also anion-active Auxiliaries and, under certain circumstances, mixtures of these surface-active agents.

The dye liquor can also contain thickeners. The thickener used in the

Textile printing well-known products, /. B. locust bean gum, Galactomannan !, tragacanth. Solvitosi. ·. Polyvinyl alcohols or British gum or the water-soluble salts of alginic acids. But Fs can also cellulose derivatives, such as methyl cellulose or Find synthetic salts of carboxymethyl cellulose use.

At the start of the dyeing process, the I ärbcbad with advantage a temperature of about 40 "C, then the temperature is increased and dyes while I ¹ J to 90 minutes, preferably about 60 minutes, at a temperature of about 70 to 100'C. preferably at 95 to 100.degree. C. It is also possible to dye in closed vessels under pressure and at temperatures above 100.degree. C., expediently between 110 and 140.degree. C., using what is known as the single-hole temperature process.

The fleet ratios are 1: 1 to 1: 100. preferably 1:10 to 1:50. The colored material is then washed and dried as usual.

The fiber material can also be continuous, i.e. H. are colored by impregnation with suitably thickened aqueous dye preparation, the Fixation of the dyes by post-heat treatment, z. B. by steaming at temperatures \ on 98 to I Oj (with neutral saturated steam or heat setting at 180 to 210 ° C. If so desired the impregnated goods can first be dried or in a closed vessel at normal or stored at elevated temperature and then steamed at atmospheric pressure or direct pressure.

The new dyes are particularly suitable for printing on the materials mentioned. One prints in in the customary manner, optionally using the customary abovementioned thickeners on textile fabrics of animal or vegetable, natural or synthetic origin, on fiber materials made of plastics or glass, on wallpaper or paper. If so desired Can binders made from aldehydes, especially formaldehyde and phenols or products made by Condensation of urea, its derivatives or analogues or aminotriazines with aldehydes, optionally obtained in the presence of monohydric or polyhydric alcohols, and also condensation products from saturated aliphatic dicarboxylic acids and tri- or polyhydric alcohols with at least 3 Carbon atoms are used in the printing pastes.

The printing itself takes place on known machines, such as. B. on a roller printing machine. Rotary printing machine, stencil printing machine or film printing machine. After printing will be the material dried, subjected to a fixing process and then finished by rinsing.

The fixing of the dyestuffs is effected depending on the type of fiber, for example at 98-120 ⁰ C with water vapor with or without pressure, in particular for 20 minutes with saturated steam at 100 ° C or preferably with dry air of about 190 to 21O ⁰ C for 30 to 60 seconds . But it is also possible to carry out the fixing process with superheated steam for about 5 to 10 minutes at 160 to 200.degree. In certain cases, the printed fiber material can only be stored in the moist state for at least one hour at temperatures of 15 to 45 ° C.

The new dyes can also be used by means of a thermal. Transfer printing process onto the textile

UTidl transferred. If necessary, thickened coloring paste!) Are combined. Auxiliary carrier, / B. Pap-jr or aluminum foil, aufchraelit, for example by creating:. 'Ise or gaiizflächenigcs spraying, coating or expediently by printing. After the carbide is applied to the inert carrier, it is dried, B. with the help of a warm air siromcs and infrared radiation. The treated supports are then brought into contact with the textile material and si; for a long time at 100 to 2 ¹ K) C., preferably 180 to ¹ 210 "C., until the transferable dyes applied to the auxiliary carrier have been transferred to the textile material. 5 to 60 seconds are usually sufficient.

The exposure to heat can be done in a number of known ways, e.g. B. by passing a hot heating drum, a tunnel-shaped heating zone or by means of a heated roller, advantageously in Presence of a pressure-exerting, unheated or hphrt7trn fjpcrpnu / ni? * »** ijer siries are called Killsndcr'i or by means of a heated plate (iron or was. ie press), optionally under vacuum, the by steam, oil. Infrared radiation or microwaves are preheated to the required temperature or are in a preheated heater.

The new dyes are water-soluble. They are distinguished by the fact that they are one under dyeing conditions Contain a deductible group which contains at least one have water-solubilizing remainder. Depending on the substrate, both the inventive water-soluble dye as well as the corresponding water-insoluble dye resulting therefrom as draw such on the fiber material. The dyes according to the invention have the advantage that they split off surface-active compounds during dyeing and printing, which a priori during dyeing Egp.lizing effect and the necessary surface activity for wetting the fiber surfaces bring in. In most cases, there is therefore no need for dyeing and printing with the ben according to the invention Dyes the use of additional surface-active agents such as dispersants, emulsifiers, Wetting agents and similar auxiliaries. This way of working thus provides the additional advantage of a considerable reduction in wastewater load .ng. In addition, the dyes according to the invention are distinguished from the water-insoluble dyes the same chromophoric system by achieving much stronger color prints on natural and synthetic fibers and thus a variety of fiber types due to better affinity / υ.

In the following examples, the present Invention explained further, but without restricting it to the scope of the examples. The Prozer. ^ are percentages by weight.

example 1

a) 20 g of a copper phthalocyanine dye of the formula

V ^ INIt - L M Λ llj'l, l / (

are suspended in 200 ml of ethanol and treated with 20 g of paraformaldehyde. You then make the mixture with triethanolamine to a pH value of 10 to 12 and leaves it for 5 hours at 60'C react. The reaction mixture is then adjusted to pH 7 with glacial acetic acid. The obtained methylolated Dye compound is made by evaporation at 40 to 60 "C under a reduced pressure of 11 mm Hg from the excess formaldehyde and the solvent freed and dried at 40 ° C. in vacuo. 27 g of a resinous methylolated dye compound are obtained. Instead of triethanolamine, triethylamine or sodium hydroxide can also be used as the basic catalyst be used.

b) 6.34 g (0.01 mol) of the dye methylolated according to a) are mixed with 4.4 g (0.1 mol) of ethylene oxide and 100 mg of Ta (OC ₂ H *;) .; melted in a glass tube. The reaction mixture is allowed to react for 16 hours at a pressure of 8 μl and with shaking in an oil bath thermostatically stabilized at 80.degree. 10.2 g of a water-soluble phthalocyanine dye of the formula are obtained

CiI ₂ O ICH ₂ CH ₂ O) _x --H

CH ₂ O - ICH ₂ CIU) I, Il

ClCH, -CiI, - NSO ₂ SO ₂ - N CH ₂ CH ₂ Cl

Cl-CH ₂ -CW ₁ N-SO ₂ - CuPc - SO ₂ N -CH ₂ Cl ₂ Cl

^: CH ₂ O - (CH ₂ CH ₂ Oh H.

CH ₂ O - (CH ₂ CH ₂ Ot; - H ν - ν - u- - ζ - ■ 10

Yield: 95 ° O of theory.

The following table contains further water-soluble dyes according to the invention, which can be found in Use of the embodiments described in Example 1 under a) and b) is obtained if one first methylolated the dyes in column 2 and the corresponding N-methylol compounds in the in Column 5 indicated temperatures with the alkylene oxides of column 3 in the presence of the catalysts in column 4, in column 6 of the table are the obtained yields of the new dyes in g and weight percent of theory aneeeeben.

Table

example No.

I (irmel No.

Mill J 8.8 Mn! A. C. Howl ■: ■ " 0.01 11.0 0.2 U.I g of catalyst B. 81 0.01 Ethylene oxide 13.2 0.25 80 11.5 8th( 5.0 0.01 U 11.0 0.3 Ta (OCiH ₅ ), 80 15.8 8th( 5.0 0.0! 13.2 0.25 Ta (OC ₂ H ₅ ), 80 18.3 9! 5.0 0.01 8.8 0.3 Ta (OCiH ₅ J ₅ 80 20.0 9! 8.5 0.0! 13.2 0.2 Ta (OCjH ₅ ), 80 22.0 u; 8.5 0.015 8.8 0.3 Ta (OCiH ₅ ), 80 16.2 9 ' P.5 0.05 13.2 0.2 Ta (OCiH ₅ ) S 80 29.0 8 < 16.0 0.05 15.4 0.3 Ta (OC ₂ H ₅ J ₅ 80 14.2 9 ' 7.14 0.05 i 3.2 0.35 Ta (OC ₂ H ₅ Js 80 20.2 9 ' 7.14 0.0 i 17 6 0.3 Ta (OC ₂ H ₅ ), 80 22.5 9; 7.14 0.01 13.2 0.4 Ta (OC ₂ H ₅ ), 80 22.0 9! 9.0 0.01 17.6 0.3 Ta (OCjH ₅ ), 80 26.2 9; 9.0 0.01 13.2 0.4 Ta (OCiII ₅ ), 80 21.6 9; 9.0 0.005 17.6 0.3 Zr (OCiH ₄ CI) ₄ 80 26.0 9 ^l 9.0 0.005 13.2 0.4 Zr (OCjH ₄ CD ₄ 80 22.9 9 · 9.6 0.005 11.0 0.3 Ta (OC ₃ H ₅ ), 80 27.0 9i 9.6 0.005 5.0 0.25 Ta (OC ₂ HO, 80 22.0 9 < 9.0 0.005 8.8 0.12 Ta (OC ₂ H,), 70 20.0 9 < 10.0 0.005 8.8 0.2 Ta (OCjH,), 70 15.0 X: 10.0 0.005 11.0 0.2 Ta (OCjH ₅ ), 80 13.0 9: 4.x 0.01 8.8 0.25 Ta (OC ₂ H ₅ ), 80 13.1 9f 4.5 0.01 15.0 0.2 Zr (OCjH ₄ CD ₄ 80 18.0 9 < 7.25 0.01 6.6 0.325 Ta (OCjH,), 80 17.8 9 ^l . 9.0 0.01 11.0 0.15 Ta (OC ₂ II ₅ I ₅ 70 23.0 9 ( X.O 0.01 13.2 0.25 Ta (OCjH ₅ ), 70 13.5 9f 7.25 0.012 6.6 0.3 Ta (OCjHO ^ 70 18.0 9S 7.25 0.01 11.0 0.15 Ta (OCjH,), 50 23.0 9 ' 9.6 0.01 8.8 0.25 Ta (OCjH ₅ ). 70 13.8 9 ( X.O 0.02 11.0 0.2 Ta (OC ₂ HO, 70 18.5 8th" X.O 0.02 8.8 0.25 Ta (OC ₂ IlO ₅ 80 15.5 9: X.6 0.01 8.8 0.2 Ta (OC ₂ H ₅ ), 80 19.2 9 ( X 6 0.02 I 1.0 0.2 Ta (OCjH,). 80 11.8 9 ( 4.3 0.02 15.4 0.25 Ta (OCjIlO, 80 17.0 Ψ 8.9 0.02 13.2 0.35 Ia (OCjIlO. 80 20.0 9> 8.9 0.04 13.2 0.3 Ta (OCjIlO, 80 24 9 ( X.M 0.03 6.6 0.3 Ta (OCjIlO 80 30th T 17.X 0.015 13.2 0.15 Ta (OCjIlO, 80 26th 9 < 13.35 0.15 6.6 0.3 Ta (OCjIlO, XO 12.4 ⁱ n 6.3? 0.02 4.4 0.15 Ta (OC ₂ II ..). XO 19.2 9i 6.33 0.02 6 = 6 O.I Ta (OC, 11.1, XO 15.0 9-: X.4 4 0.0 | 5 13.2 HJS Ia (OCIh). XO 12.2 X.4 4 ii.nl- 6.6 I! .. ¹ Ta (OCiIlO, X (I. 13.7 IJ " 7.26 ('.I! ¹ 1.1 O.I S TiI (O (MlO- XIl 2 (1.0 <» 'Ill ¹ 6.6 'I.I 1.1 (OCII I XII 16. (1 Mf M. (, S Ii IP 6.6 Oh 1, HOC Il I SII I <. ^ς ') ¹ J i '. ·: 11. (I Γ> ι: ■ < (II ^k I HOCII) X (I. | \ ί Wed '·> IS "ίΐΐ - U ^: 1.H (K II.ι XO I '.' ¹ ) ^l - ".!! I, m () (Il ι Ml ¹ Il ¹ 1! I, HOC.Il I

2 XXXVIII 3 XXXVHI 4th XXXVIII 5 iXL 6th IXL 7th XXMl! X XXVHI 9 XL IO XL I I XL i 2 XLi 13th XL! 14th XLI 15th XLl 16 XXVI 17th XXM IS XXXVII 19th XXXViI 20th XXXVII 21 XLI 22nd XLI 23 LMII 24 XLl 25th xxx \ 26th I.VIII 27 LVIII 2 X XXXV 29 XXXIV 30th XXXIV 31 I. I.
L. 34 XXXIII 35 XXXIII 36 XXXIII 37 XXXIII 3 X XXXIlI 39 IX 40 IX 41 IX 42 IX 43 VIII dd VIII 1- Mil 4i. WXI \ \ \ i is WM IN THE \ \ N I.

FarhslolT 33 G 6.25 Mole 24 44 522 Mole 34 4th Application examples 58 received Dye in 2000 g of water the 0, J g des heated game 101 80 1 "," Water in a gu Dye, 0.2 ml 85% igc Formic acid 6.52 0.015 0.125 (I. I μ KaUiIv- »atiir At £ The solution is given with sec .Sodium citrate and 80 \ u> bump 96 the usual hydrosulfite developed orange hue, degree of draw 96%. aqueous solution of disodium salt / cs de Formula No. 6.52 0.015 0.125 1.5 g of the according to Hydrochloric acid to a pH Value of 3 set to 70 ⁰ C according to closed apparatus in 30 80 94 coloring game 102 XXXlII 8.9 0.015 0.125 Example warmed up. Then 50 g of polyethylene glycol g of a mixture consisting of C stains for 60 minutes 80 98 received Fiii'isct / iinu XXXlII 9.0 0.02 0.1 Tu (OCjH,). solved. repellant tissue introduced. Man the bathroom in fm pressure. 80 11.2 98 45% I. XXXIII 9.0 0.03 0.15 Nb (OC ₃ IMs By S flushed 80 11.0 96 at XXXIlI 5.58 0.03 0.3 Zr (OC ₃ II ₄ CI) ₄ Example 58 80 11.4 98 game I. 5.58 0.01 Älhylenimd 0.1 Ta (OC ₃ H,) _; In a dye liquor , 152 g one 80 13.0 89.8 No. I. 8.38 0.01 0.2 Ta (OC ₃ H,) < and 0.2 80 15th 98 50 XXXII 11.16 0.015 0.3 Ta (OC ₃ IlOs 80 22nd 96 51 XXXII 5.5 0.02 5.0 0.2 Ta (OC ₃ Hs), 80 9.7 96 52 XXXII 5.5 0.02 5.0 0.1 Ta (OC ₃ IlOs 80 14.2 9 «) 53 XXXII 5.5 0.02 5.0 0.2 Ta (OC ₃ Hs), 80 21 93 54 XIII 4.51 0.02 4.4 0.3 Ta (OC ₃ Hs), .SO 19.3 98 55 XIII 4.51 0.01 6.6 0.1 Ta (OC ₃ IlO, SO 10.3 98 56 XIII 4.51 0.01 13.2 0.15 Ta (OC ₃ Hs), 80 13.5 98 57 XII 5.83 0.01 4.4 0.2 Ta (OC ₃ HO, 80 18.5 96 58 XII 5.83 0.01 8.8 0.15 Ta (OC ₃ H,), 80 P.9 96 59 XII 5.83 0.01 13.2 0.2 Ta (OC ₃ IIs), so 11.0 98 60 XIV 5.11 0.01 8.8 0.3 Ta (OC ₃ IIs), SO 13.0 86 61 XIV 5.11 0.01 4.4 0.1 Ta (OC ₃ IlO, 80 12.0 95 62 XIV 4.52 0.01 8.8 0.2 Ta (OC ₃ HsJs 80 14.5 97 63 LI 4.52 0.01 13.2 0.1 Ta (OC ₃ HO, 80 16.5 99 64 Ll 4.33 0.01 4.4 0.2 Ta (OC ₃ HOs 80 9.2 97 65 XV 4.33 0.01 6.6 0.1 Ta (OC, Hs) s 80 13.6 96 66 XV 4.3 0.01 8.8 0.2 Ta (OC, lls) s 80 9.0 98 67 XXX 4.33 0.01 6.6 0.1 Ta (OC ₃ IlOs 80 13.0 99 68 XXX 6.8 0.01 8.8 0.2 Ta (OC, Hs) s 80 8.5 98 6 ') VII 6.8 0.02 13.2 0.1 Ta (OC ₃ Hs). 80 13.0 97 70 VII 9.1 0.02 4.4 0.2 Ta (OC ₃ H.) s 80 9.0 95 71 XVIII 9.1 0.02 8.8 0.1 Ta (OC ₃ IIs), 80 13.0 97 72 XVIII 7.1 0.02 4.4 0.2 Ta (OC, Hs) s 80 11.0 97 73 XIX 7.1 0.02 8.8 0.1 Ta (OC ₃ Hs), 80 15th 96 74 XIX 4.29 0.02 4.4 0.2 Ta (OC ₃ IlOs 80 13.2 97 75 XII 4.29 0.01 8.8 0.1 Ta (OC ₃ IIs) S SO 17.6 97 76 XII 0.01 4.4 0.7 Ta (OC ₃ IlOs 11.2 98 77 LXX 8.8 Ta (OC ₃ IlOs 15.6 ΊΑ LXX 4.4 Ia (OC ₃ IIs). Minutes r, .6 79 8.8 Ia (OCIlO, 13.0 C around 80 4.4 this temperature below 81 8.8 The coloration obtained is then with 82 4.4 on 130 < and dried. To 83 8.8 cleaning you get a 84 4.4 8.8

DGdecyldiphenylätherdisulfonsäure, 0.015 g of a compound of the formula

CH,

C ₁₁₁ H, /

IC H, CH ₂ O) ,, H

CH ₂ -CH - 0 (CH ₂ CHjOLH

η + ρ = IS

and 0.033 g of water containing, is entered at 40 ⁰ C with IO g _ls polyamide 6,6. The bath is then heated to 100 ^° C. for 40 minutes and dyed at this temperature for 1 hour. The colored product is washed with water. A level orange coloration is obtained.

Example 103 ^{! Ü}

A fabric consisting of bleached and niercerized cotton of 120 g / m ² is printed in roller printing with a printing paste, which is prepared in the following way: 2s

450 g of a 5% aqueous sodium alginate solution are with

440 g of water diluted and
30 g diammonophosphate 1: 2 added.

y ·

This solution is adjusted to a pH of 8 with triethanolamine and, while stirring, with 80 g of the according to Example 18 prepared dye mixed.

After drying, the beiirucktc tissue is exposed to 60 seconds of treatment in dry air at ⁰ C while 20G is cold and connect ^ then at 60 ⁰ C with 0.5 g / l of a nonionic Äthylenoxydproduktes soaped. The printed fabric is then rinsed with cold water and dried. A print with an intense, pure golden yellow shade is obtained.

Example 104

Proceed as described in Example 103, however using a fabric made of polyethylene glycol terephthalate fibers instead of cotton, we get 4, you also get a print of an intense golden yellow hue.

Example 105

A bleached and mercerized cotton fabric ^{with a weight of 140 g / m 2} is printed in film printing with a monochrome design using a printing paste, which is produced in the following way:

80 g of a dye prepared according to Example 43

are incorporated into a solution, adjusted to pH 8 with ammonia, of 22.5 g of sodium alginate and 10 g of ammonium chloride in 967.5 g of water. After drying, the printed fabric is fixed during I minute at 200 ⁰ C in dry hot air and subsequently, then soaped f> o cold at 6O ⁰ C using 2 g / l soap and then rinsed again cold. A print of a well developed brown shade is obtained.

Example ΙΟύ

The procedure is as described in Example 105, but using a fabric made of viscose or CH ₁ SO ₄

Polyethylene glycol terephthalate instead of cotton, so e / one also keeps corresponding prints of a well-developed brown hue.

Example 107

With 10 g of a multi-fiber tape you go into a dye liquor of 40 ⁰ C, the ratio in the liquor 1:40

3% of a dye prepared according to Example 48 contains 4% diammonophosphate.

The liquor is then heated to 95 ° C. for 25 minutes and dyed at this temperature for 1 hour. After the liquor has cooled down, it is rinsed and dried. A red color is obtained.

Example 108

A multi-fiber tape is impregnated with an impregnation liquor which contains 0.3 g / l of a dye prepared according to Example 48, 0.2 g / l diammonophosphate, 0.02 g / l of a nonionic ethylene oxide product, at 20 to 30 ° C., then squeezes one jnd to 100%, based on the dry weight of the product decreases. dried at 8O ⁰ C for 10 minutes and subsequently ßend is fixed at 190 ⁰ C during. 1 minute. wash the coloring cold, then at 50 ° C again cold and dried, giving a red color.

The multifiber tape of Examples 107 and 108 consists of cotton, cellulose, silk, nylon, polyacrylonitrile. Modacryl (Dynel), polyethylene glycol terephthalate, cellulose triacetate and cellulose acetate. The base fabric is wool.

Example 109

A cotton fabric weighing 120 g / m ² , bleached and causticized, is printed with a printing paste of the following composition:

910g of an aqueous 2.5% sodium alginate solution

sung with
10 g ammonium chloride mixed with ammonia

adjusted to pH 8. In this paste 80 g of according to Example 56 added dye obtained. After printing, as in Example 103 is given dried, fixed and washed out. A print of a well developed brown tone is obtained.

Example 110

The procedure is as indicated in Example 109, but using a fabric made of viscose or Polyethylene glycol terephthalate instead of cotton, you get corresponding prints in a good developed brown tone.

Example 111

Mercerised cotton fabric is impregnated on a foulard at 4O ⁰ C with a liquor having the following composition:

40 g / l of the dye obtained according to Example 58
100 g / l 2.5% aqueous sodium alginate solution and
2 g / | Dibutyl-naphthalenesulfonic acid sodium salt

and 85% formic acid to achieve a pH value of 2.8. The squeezed to approximately 100% of the product weight tissue fixed for 2 minutes at 100 ⁰ C dried and then for 90 seconds at 210 ⁰ C. The dyed goods are rinsed with water, soaped and dried. A strong orange coloration is obtained. If the procedure is as indicated in Example 111, but using a mixed fabric of polyethylene glycol terephthalate and cotton (33:66), an orange coloration is also obtained.

Example Π2

A fabric consisting of bleached and mercerized cotton of 120 g / m ² is stenciled with a printing paste that is prepared as follows:

25 g of a sodium alginate compound are introduced into 760 g of water with vigorous stirring. Thereafter 100 g of the mixture prepared according to Example 49 are first added to the resulting pulp, always with vigorous stirring Dye, then 10 g of a partially etherified melamine-formaldehyde precondensate and 15 g of one 2-A mino-2-methylpropanol hydrochloride compound attached.

After drying, the printed fabric is subjected to a treatment in hot air at 150 ^° C. for 5 minutes, the synthetic resin being crosslinked. The printed fabric is then rinsed cold, boiling for 5 minutes and cold again and finally dried. A print of an intense red shade is obtained.

Example 113

Proceed as described in example 112, however using a fabric made of polyethylene glycol terephthalate fibers instead of cotton, so obtained one also has a print of an intense red hue.

Example 114

100 g of the dye prepared according to Example 58 are mixed by stirring in 900 g of a paste prepared in the following way:

25 g sodium alginate powder are added by slowly sprinkling into 925 g water and using a high speed stirrer to a viscosity of the preparation brought by lOOOOcP. Then 50 g of one high-boiling gasoline fraction (boiling point 120-180 "C) emulsified into it.

In the screen printing process, a weakly sized paper with a basis weight of 70 g / m ^{2 is} printed with the above printing ink paste. The printed paper is dried at room temperature. On the thus-treated paper support placing a fabric made of polyethylene glycol terephthalate, and then brought into contact by means of a heating plate support and fabric for 30 seconds at 21O ⁰ C. The dyed fabric is then separated from the carrier. In this way, a strongly colored, yellow-brown print is obtained which has excellent wet fastness.

Claims (1)

Patent claims: 1.Water-soluble, alkoxyated dyes of the general formula (la) or (1b) F - / - X ₁ -N - CH, - O- Z \ Ha)
R. a) a methylol derivative of the general formula