DE2444522A1 - HYDRO-SOLUBLE ORGANIC COLORS AND OPTICAL BRIGHTENERS - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basel

QBA-GEiGY

Case 1-9015 / + Germany

Water-soluble organic dyes and optical

Brightener

The invention relates to new intermediate water-soluble, organic dyes and optical brighteners, their production and their use for dyeing or optical brightening and printing of natural products and synthetic organic materials.

509817/1032

The new organic dyes and optical brighteners are characterized in that they are at least have a hydrophilic ether group derived from polyols which has the general structure via the grouping

N - CH ₂ - 0 -

is bound to the dye or brightener skeleton, wherein the nitrogen to an acid amide group of the dye or. Brightener molecule belongs and the oxygen is bound to the hydrophilic ether residue.

Advantageous water-soluble organic dyes and optical brighteners of the present invention are thereby characterized in that they contain at least one nonionic water-solubilizing group of the formula

(1) - X ₁ - N - CH ₇ - 0 - Z

in which -X -.- N- represents an acid amide radical which is connected to the dye or Aufheilergerüst via X, or N or is part of such, X, the divalent bridge -CO-, -CS-, -CNH- or -SO ₂ - or a carbon atom which is part of a nitrogen heterocycle and is adjacent to the ring nitrogen, Z is an optionally substituted mono- or polyalkylene glycol radical with an average molecular weight of at most 2500.

509817/1032

By definition, the end substances contain at least a non-ionic water-solubilizing group of the type mentioned. Depending on the structure of the used Starting components contain several such groups, which are terminal or in the dye- or brightener molecule can be built-in amide groups.

Depending on the way in which the grouping of the formula (1) is bonded to the dye structure, the following basic types are of particular interest.
A. Compounds of Formula

(2) ^ _12n
R.

wherein F is the residue of an organic dye, η 1 to 6, preferably 1 to 4, -X - N- an acid amide residue, R

Signify hydrogen or an organic radical and X,

and Z have the meaning given. B. Compounds of the formula
(3)

wherein F and Z have the meaning given, X ₂ -CO- or -SO, - and R .. an optionally substituted and / or via an oxygen atom or an amino group on bonded hydrocarbon radical and n-, 1 to 3 mean.

509817/1032

The polyols are compounds with at least two hydroxyl groups, for example Alkylene diols with 2 to 4 carbon atoms or polyalkylene glycols with 2 to 50, preferably 5 to 30 alkyleneoxy groups, of which individual alkylene groups are replaced by alkyl with 1 to 3 carbon atoms, preferably methyl,

Phenyl or glycidyloxy substituted and their terminal ones Hydroxyl groups with an alkanol of 4 carbon atoms or less can be etherified.

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

The remainder Z is above one of its oxygen atoms

bound to the methylene group. Is the alkylene glycol residue substituted, it can be on individual alkyleneoxy groups, preferably have on ethyleneoxy groups »phenyl, alkyl with 1 to 3 carbon atoms or glycidyloxy radicals.

These alkylene glycol radicals can also be terminal be etherified with an alkanol with a maximum of 4 carbon atoms, e.g. with n-butanol, n-propanol, ethanol or especially methanol. However, the unsaturated products are preferred. The remainders Z derive e.g. from Ae thy I en-

509817/1032

glycol, diethylene glycol, optionally by methyl, phenyl or glycidyloxy-substituted polyethylene glycols, 1,3-propylene glycol, 1,2-propylene glycol, polypropylene glycol, Polybutylene glycol, polypropylene polyethylene glycol.

In formula (2), R preferably denotes hydrogen or an alkyl radical having 1 to 4 carbon atoms, which can optionally be substituted with halogen, cyano, hydroxyl or alkoxy having 1 to 4 carbon atoms. Of the Substituent R can also be part of a nitrogen hetero ring in which the groups -CO-, -CS- and

_/ C = NH can be included, as in derivatives of the unsubstituted in the 1-position 5-pyrazolone or 5-aminopyrazole or barbaric acid or cyanuric acid, such as 2,4,6-triamino-substituted or 4-hydroxy-2, 6-diamino-substituted pyrimidine or triacine derivatives or their ethers. If desired, R can also have a second grouping -CH _? -OZ represent. In formula (3), R-, preferably a

. 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 with 1 to 4 Carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, hydroxyl, amino or nitro groups ring-substituted can be.

509817/1032

Depending on the type of starting components used to prepare the dyes according to the invention, the grouping of the formula (1) can be linked to the dye molecule directly or via any desired bridge members. The bridge members are, for example, divalent hydrocarbon radicals, for example lower straight-chain or branched alkylene radicals, such as the methylene, 1,2-ethylene or 2,2-propylene group, the 1,1-cyclohexylene group or lower alkenylene radicals, such as the vinylene group, also ether groups, thioether groups, aminoalkylene or amido, and substituted or unsubstituted imino groups into account, the latter methylolierbare ureido, thioureido or Guanidingruppierung may form ^s.

The water-soluble organic dyes and optical brighteners of the present invention are preferably thereby manufactured that one organic dyes, optical brighteners or dye precursors, which at least one free methylol group attached to an amide nitrogen have, with an alkylene oxide in the presence of a metal alcoholate a transition metal of groups IV, V or VI of the periodic table and optionally an alkali metal hydroxide or alkali metal alcoholates and, in the case of the use of dye precursors, these by conversion with the other dye component to the corresponding

509817/1032

completes the final dyes.

If the amide nitrogen contains a second —CH ₉ OH, this methylol group can also be etherified according to the invention.

It is particularly advantageous if one starts from organic dyes or dye precursors which at least one N-methylolated carboxamide or sulfonic acid amide group exhibit.

The N-methylated dyes, optical brighteners or dye precursors used as starting components are prepared by reacting corresponding dyes, optical brighteners or dye precursors which contain at least one amide group which can be methylolated with formaldehyde or a formaldehyde-releasing compound. Suitable formaldehyde donors are, for example, trioxane, hexamethylenetetramine, but preferably parafortnaldehyde. The reaction of the dyes containing amide groups with formaldehyde or formaldehyde-releasing agents is generally carried out in an aqueous or aqueous-organic medium, but preferably in an organic medium at temperatures from 40 to 100 ^° C.

The basic dyes, in which at least one nonionic water-solubilizing agent according to the present process Grouping is introduced can be the most diverse classes belong. These are, for example, given

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244452

if metal-containing mono- or polyazo dyes, including formazan dyes, to azomethine, methine, Anthraquinone dyes, as well as 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 as well polycyclic higher condensation dye systems from the series of benzanthrones and dibenzanthrones and their condensation products. If these dyes contain groups which form metal complexes, for example in the series of Mono- or polyazo and azomethine compounds, the dyes can often be advantageously in the form of their corresponding 1: 1 or 1: 2 metal complex compounds, such as Use copper, cobalt, chromium, iron and nickel complexes. Among the azaporphine dyes have because of them comparatively easy accessibility the phthalocyanine dyes of preferred interest. These can be as Metal-free compounds as well as with complex-bound metals e.g. as cobalt, copper and nickel phthalocyanines, Find use. Also suitable for the inventive Process also pigment dyes from the isoindolinone series and anthraquinone dyes, e.g. in the German Patents 1,098,126, 1,148,341, 1,111,317, 1,154,212,

509817/1032

1,189,669, 1,644,541, 1,644,542, 1,644,543, 1,644,539, and 1,644,540.

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

The defined nonionic hydrophilic ether group can also be used in optical brighteners, the one methylolatable acid amide group are introduced. These optical brighteners can belong to any class. In particular, it is methine, azamethine or Stilbene compounds, coumarins, pyrazines, pyrazolines, oxazines, Dibenzooxazolyl, benzofuran or benzimidazo compound s, which preferably have a terminal sulfonic acid or carboxamide group or a 4,6-diamino or Have 2-alkoxy-4-aminotriazinylamino group.

In addition to the acid amide group required to introduce the nonionic hydrophilic group as defined can use the dyes and dye precursors mentioned be further substituted in the usual way. As further substituents are 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, trifluoro

509817/1032

methyl, 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 such as alkoxy, such as methoxy, ethoxy or phenoxy or benzyloxy groups, amino, alkylatnino, aralkylamino, arylamino, acylamino such as acetylamino and benzoylamino optionally Ν, Ν-carboxylic acid and disubsüituierte SuIfonsäureamidgruppen, acyl groups, such as lower alkanoyl, aroyl, alkoxycarbonyl, ALK3 ^T lsulfonyl- or arylsulfonyl groups, SuIfonsäurealkyloder-aryl ester, further Reactive groups such as halotriazinylamino or amido groups, halopyrimidinylamino or amido groups, esterified hydroxyalkylamino or amido groups, haloalkylamino or haloacrylamino groups, vinylsulfone, sulfochloride, esterified hydroxyalkylsulfone groups, and optionally acroylamino groups which are substituted by alkyl or halo wi e sulfonic acid, carboxylic acid, phosphoric acid groups or acylated sulfonic acid amide groups and onium groups, such as ammonium, including the cyclammonium, sulfonium or phosphonium groups. The aromatic rings which may be present in these substituents can in turn be substituted in the same way.

50981 7/1 032

Particularly preferred dyes, dia at least one for the introduction of the nicbtionogenic according to the definition have hydrophilic group required acid amide grouping, are derived e.g. from the following compound classes:

a) monoazo dyes of the formula

(4)

in which D is the remainder of a diazo component, especially of the benzene series, Ar is an arylene residue, especially an optionally substituted 1,4-phenylene radical, R2 and R ^ each one optionally substituted alkyl group and B the remainder of a coupling component, e.g. of phenol, Acyl acetic acid amides, 5-pyrazolones, 5-aminopyrazoles or hydroxypyridones »a I or 2 mean, where at least one of the radicals D, Ar,

B, R ₀ and R- an acid arid group of the formula -X ₁ -K ¹ H ZJ 1,

contains, where "" ^R

_ ·· - · _ ■■ 'χ ühd R the given under formula "(2) Have meaning, contains.

To this. Azp dyes only belong to the methylolation capable acid amide group-containing dyes of formulas (5) to (11): "

509817/1032

(5)

/ R, N = N-Ar-N

worii "» R, an optionally substituted alkyl or aryl radical and Q the group -CONH-, -SO ₂ NH-, -NH-CO- or -NH-SO ₂ - and the ring A still further non-water-solubilizing May contain groups, for example cyano, nitro, halogen, alkoxy with 1 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms Ar, R ₂ and Ro have the meanings given above.

(6)

where R ₂ and Rl denote alkyl radicals which cannot contain water-solubilizing groups> and Rl can also be hydrogen and G represents an optionally substituted alkylene radical. A, Q, Ar, R ₉ and R ~ have the meaning given.

(7)

wherein B, a residue of the coupling component of the phenol, Enol - e.g. acyl acetic acid arylamide, pyrazolone, aminopyrazole

or hydroxypyridone series represents. A, Q and R, have the specified Meaning;

509817/1032 "minal inspected

o \ / J

(8) ^Z NG- (M 'A

^R 3

where the symbols have the meaning given. (9) D-N = N-Ar-N

in which G ₁ denotes an alkylene group which is optionally interrupted by heteroatoms, especially oxygen atoms, and D, Ar, Ry and X ~ have the meaning given.

f, (10) DN = N

where D, R ₂ , R ₃ , R /, X ₂ are as defined above and L is hydrogen, halogen, for example chlorine, alkyl groups with a maximum of 4 carbon atoms, alkoxy groups with a maximum of 4 carbon atoms, phenoxy, phenylthio or alkoxycarbonyl with a maximum of 5 carbon atoms;

(11) DN = NB ₉

ORIGINAL INSPECTED

509817/1032

where D has the meaning given and B _{9 is} the residue of a methylolatable N-heterocyclic coupling component, for example a residue of barbituric acids, 2,4,6-trisubstituted pyrimidine, especially 2,4,6-triaminopyrimidine, 6-hydroxy-pyridones, 3,5-dioxopyrazolidines or 4-hydroxy-2-quinolones, which may contain the substituents listed above which are customary in azo dyes;

b) disazo dyes of the formula

(12) DN = N ~ / Ä \ - N = N / Ar - <^ ² ) (B) ₂ _ _a

in which D, A, Ar, R ₉ , Rn and a have the meaning given and where at least one of the radicals D, Ar, B, R ₀ and Ro is an acid amide group of the formula -X ₁ -NH, in which

Zo 1 I _R

X, and R have the meaning given contains.

ORIGINAL INSPECTED

509817/1032

c) Disazo dyes (pigments) of the formula ^

(13) CO-Ar ₁ -N = NB ₁₃ -N = N-Ar ₀ -CO

NH-R ₁

NH-R _r

where B- denotes the radical of a coupling component containing two enolizable ketomethylene groups, Ar ₁ and Ar «denote an aryl group free of hydroxyl groups and Rj denotes an optionally substituted aryl group j, especially from the benzene series.

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

(14) CO-Ar ₁ -N = N-CH-CONH-R ^ -NHCOCh-

I ¹ I ⁶ I.

N = N-Ar ₀ -CO ¹ I

NH-R _r

COCH,

COCH,

NH-R.

where R / - for arylene radicals, especially optionally halogen, alkyl or alkoxy substituted phenylene radicals and Ar., Ar2 and · R_ have the meaning given.

d) Disazo dyes (pigments) of the formula

(15)

CONH-T ₃ -NH-CO. "

N = N-T,

509817/1032

where T, and T _2, independently of one another, are each a phenyl radical which can be substituted, for example, by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, cyano, nitro and alkylsulfonyl having 1 to 4 carbon atoms and T- one optionally arylene radical substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen, especially of the benzene series, such as, for example, a phenylene or diphenylene radical.

d) Anthraquinone dyes of the formula

Y ,. 0

(16)

wherein E is halogen, especially bromine or chlorine, or alkyl or alkoxy, especially methyl or methoxy, m 1 or 2 and Y ,, Y ₂ , Yo and Y, each hydrogen, an optionally substituted by an alkyl, aralkyl, cycloalkyl, Aryl or heterocyclic radical substituted amino or hydroxy group or a nitro group, where one of the symbols Y ,, Y «, Y or Y / or the anthraquinone nucleus itself is an amide group capable of introducing the nonionic water-solubilizing group, especially a carboxylic acid or sulfonic acid contains amide group.

© FslSIMAL \ KZ? = ~

509817/1032

Typical representatives of the abovementioned classes of dyes are: α) monoazo dyes

α,) disperse dyes

OH

(I) CH ₃ CONH-

N = N

CH,

(II) O ₉ N- / VN = N-

(Ha)

'NHCOCH,

C = N

CH

NHCOCH,

I- / V-W = KT-

CoH

2 "5

509817/1032

(Ill)

Cl

OCH,

N = N

, ^Ν

NO ₂ NHCOCH ₃

NH-CO

CH ₂ CH ₂ O-CH ₂ CH ₂ CN

. NHCOCH ₂ CH ₃ R _x =

H 60%

OH

CONH

fV- N ^

(VII)

NH ₂

NHCOCH,

509817/1032

Cl

(viii) ο ₂ ^Ν "Λ / ^{Ν == Ν}

/ ^C 2 ^H 5

Cl CH,

C ₂ H ₄ CONH ₂

CH, C ₂ H ₄ CONH ₂

NO

,OH

(X) CH- -f VN = N-C = C

C = N CONHo

NH-

Cl

O ₂ N-

-N - C

NO, C-NH-

NHCH ₂ CH ₂ OH

^C 2 ^H 5

CH

(XlI) ff \ —N = N- C = C /

OH SO ₂ NH ₂

509817/1032

(XIII) ( VNN - CH

CO - NH

-CO

CO-NH

(XIV)

OC ₂ H ₅

l ~ NH

N = N-CH

CONH

OC ₂ H ₅

Cl

(XV)

^H 3 ^C /

NO

CO

[—CH \

(XVI)

NH2

Cl

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OCH,

(XVII)

Cl

= N_ CH - CONH

CH.

COCH ₃ OCH ₃

Cl

(XVIII)

CH ₀

I ³

C = N-

-N = N

(XIX)

N = N-

CH _Q

I ³

C = N I

OH

SO ₂ NH ₂

ORfGJNAL JNSPECTED

509817/1032

Wool dyes

OH «« ^cl

(XX) | * ^i? SpN = N-

1: 2 cobalt complex

(XXI)

HO Cl

1: 2 chromium complex

(XXII)

OH

OH

-N = N HN

O ₂ SCH ₃

N = N-T, H-CH

H N

COOCH, CH ₃ -SO ₂

HO

Cl

1: 2 mixed chrome complex

509817/1032

α.) Cellulose dyes

SO ₃ H

(XXIII)

N-N

^H0 3 ^S SO ₃ H

(XXIV)

SO ₃ H

HO ₃ S

N = N

egg

N N

NH-c C-NH ₀ \ / ^Δ

N

SO ₃ H NH-CO-NH ₂

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Pigment dyes

(XXVI)

(XXVII)

/ Λ_ »~ ι

/ ^C0CH 3 OCH, CH J

'CONH- (' 'V-Cl

OCH,

(XXVIII)

OCH,

N = N

CF.

CONH

OH

st

CONH

H- ^ V-

NHCO

INSPECTED

509817/1032

- fcr-

(XXIX)

N-f V-f V CONH 0

ORlGJMAL INSPECTED

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β) disazo dyes

β,) disperse dyes

OCH ₃

(XXX) CH ₃ COM- / V- N = N- / V- N = -N- / V-OH

CH ₀

(XXXI)

N = N-f V-N

(XXXII)

/ ^C 2 ^H 5

CH

SO ₂ NH ₂

2 \ _

NO,

(XXXIIa) f ~ \ - N = N - / ~ \ - N = N -CH CO-NH

CO

CO-NH

CH.

(XXXIII) /

^C0NH

HO "

509617/1032

ß ₂ ) pigment dyes

(XXXIV)

α ei

-N = N-CH-CONH- / V- NHCOCH - N = N

Cl

Cl

COCH,

CH,

COCH,

Cl

Cl

Cl

(XXXV)

NHCO

_cl

NO,

(XXXVI)

Cl

N - N - CH - CONH COCH ₃

CO ι

NH

Cl

CH,

Cl

NHCO-CH-N = N-,

COCH,

CO ι

nh

Cl

5 0 9 81 7/10 3 2 ORIGINAL INSPECTED

(XXXVII)

Cl

N = N-CH-CO-NH-

CO

NH

Cl

NHCOCH-N =

CH ₃ COCH ₃

H ₀ C

Y N

CO

NH

(XXXVIII)

CONH-

NHCO

COOCH ₂ CH ₂ Cl

COOCH ₂ CH ₂ Cl

(IXL)

ORlGiMAL INSPECTED

509817/1032

(XL)

- ίαβ- -

H ₃ C Cl

co-HN- / 3

N = N-CH-CONH Cl CH ₃ A-NH-CO

CH.

Cl

NHCO-CH-N = -N

CO-CH _n Cl

CO-CH _n Cl

(XLI)

Cl

ORIGINAL INSPECTED

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γ) Anthraquinone dyes

0 OH

NHCOCH ₂ CH ₃

0 NH

HN

CONH,

0 NH-CH

CH

CONIL

HN

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O NHCO

(LIII)

0 HNCO- / V- Cl

0 NH

CONH,

0 HN

ORfGiMAL INSPECTED

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(LVI)

(LVII)

V-CO-HN 0

HN-C

I 0 N C-HN

N 0

NH-CO-

(LVIII)

NH- CO-

ίΛ

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Phthalocyanine dyes

(LX) CUPc- (SO ₂ NH-CH ₂ CH ₂ -Cl) ₄

^ (SOoNa) ο η (LXI) CuPc

"* - (SO ₂ NH ₂ ) _1-

^ ₃₂₁ (LXII) CuPc

"^ (SO ₂ NH ₂ ) ₂ _

(LXIII) CuPC (SO ₂₂₃

(LXIV) CuPc

ORiGiMAL INSPECTED

509817/1032

C) Other dyes

(LXX)

(LXXI)

/ V NH-Q-SO ₂ NH -Q)

NH

CO-NH —ί

NO,

(LXXII)

CONH,

Cl

(LXXIII)

Cl

Cl

ΝΗ

Cl Cl

Cl Cl

Cl

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Optical brighteners

(LXXX.)

.N = C-

/ Λ-

Cl

/ Λ

-N

(LXXXI)

OCH

NN
I Il
-C, ^ C-NH

SO ₃ Na

CH = CH- ^

SO ₃ Na

C-

Il

OCH.

(LXXXII)

CH = CH-

/ Λ-ΖΛ-rTR =

CH = CH-

SOONH

AlUiA

SOONH

2

OTED

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Intermediates

.C ₂ H ₅

C ₂ H ₅

NHCOCH,

Cl

Cl

Cl

NH

CF

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Among the for the inventive etherification of the color or the optical brighteners /

Substances or the dye precursors / possible ones Alkylene oxides are compounds which have an epoxy group to be understood. This is preferably to alkylene oxides of the formula

(17) CH ₉ - CH - R ₇

whereRy is hydrogen, alkyl with 1 to 3 carbon atoms, phenyl or a CH ₉ - CH -0 ~ radical. Examples

for such alkylene oxides are ethylene oxide, propylene oxide, Styrene oxide or diglycidyl ether. Propylene oxide is preferred and especially ethylene oxide.

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

(18) 'Me (O-Ak) ₁ . (R ₈ ) _q _ _r

wherein Me is a q-valent transition metal of groups IV, V or VI of the periodic table, Ak phenyl, benzyl, cycloalkyl with at most 12, in particular 5 to 12, especially 8 to 12, ring carbon atoms, haloalkyl with 2 to 4 carbon

ORtGiNAL INSPECTED

509817/1032

V444522-

atoms or preferably alkyl with 1 to 4 carbon atoms, Rg halogen or alkoxy with 1 to 4 carbon atoms, r 1 to q and q are 4, 5 or 6. Halogen substituents are, for example, bromine or, preferably, chlorine.

These metal alcoholates are in particular alcoholates of transition metals of the groups IV, V or VI of the 4th, 5th or 6th period of the periodic table according to Lange's Handbook of Chemistry, 10th edition 1967, pages 60 and 61. For these transition metals, also called elements of the intermediate groups, the groups a or the groups b, include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. The remainder -O-Ak is preferably a radical of an alkanol such as methanol, ethanol, ß-chloroethanol, isopropanol, n-propanol, n-butanol, sea- or tert-butanol, or also phenol, benzyl alcohol or from a cycloalkanol with suitably 5 to 12 carbon atoms, like cyclododecanol. As an alkoxy, Rgin is the Usually different from -O-Ak and can e.g. methoxy, ethoxy, Propoxy or preferably tert. Mean butoxy. The reaction with the alkylene oxide in the presence of metal alcoholates is preferred the formula

(19) Me ₁ (O-Ak ₁ )

where Me ₁ zirconium ^IV , niobium ^V , tantalum ^V , tungsten ^VI or molybdenum ^ ¹ , Ak-. Alkyl of 1 to 4 carbon atoms or haloalkyl

509817/1032

^ 444522

with 2 to 4 carbon atoms and q 4, 5 or 6 mean according to the valence of the metal, carried out. Particularly suitable metal alcoholates correspond the formula

(20) Me ₂ (O-Ak ₁ )

where Me _{2 is} zirconium, niobium, tantalum or tungsten and q is 4, 5 or 6 according to the valency of the metal and Alc has the meaning given.

The reaction with the alkylene oxide is preferably carried out in the presence of an additional catalyst, namely in the presence of an alkali metal hydroxide or alkali metal alcoholate with an alkanol with 1 to Carbon atoms. Examples of such catalysts are lithium, sodium, potassium, rubidium or cesium hydroxide or the corresponding alcoholates of alkanols ^ as indicated for the alcoholates of the transition metals into consideration.

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

• The metal alcoholates alone or together with the

509817/1032 ^origin al inspected

Alkali metal hydroxides or alcoholates are advantageous in amounts of 0.05 to 5%, preferably 0.1 to 2% or in particular 0.4 to 1%, based on the weight of the reaction mixture used.

If the two types of catalyst are used together, the weight ratio of transition metal alcoholate is to alkali hydroxide or alcoholate generally 9: 1 to 1: 9, preferably 4: 1 to 1: 4 or especially 7: 3 to 3: 7.

Suitable examples of transition metal alcoholates are:

(21.1) Ta (OCH.) C (21.2) Ta (OC ₂ H ₅ ) ₅ (21.3) Ta (O-CH (CH ₃ ) ₂ ) ₅ (21.4) Ta (OC (CH ₃ ) ₃ ) ₅ (21.5) Ta (O- ^) ₅ (21.6) Nb (OCH ₃ ) 5 (21.7) Nb (OC ₂ H ₅ ) ₅ (21.8) Nb (O-CH (CH ₃ ) ₂ ) ₅ (21.9) Nb (OC (CH ₃ ) ₃ ) ₅ (21.10) Nb (O-O),

(21.11) W (OCH ₃ ) ₆

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(21.12) -W (OC (CH ₃ ) ₃ ) ₆

(21.13) Hf (O-CH (CH ₃ ) ₂ ) ₄

(21.14) Hf (O-C (CH.).),

OO * ~ τ

(21.15). Mo (O-CH (CH ₃ ) ₂ ) ₆

(21.16) Mo (O-C (CH ₃ ) ₃ ) ₆

(21.17) Ti (OC ₂ H ₅ ) ₄

(21.18) Ti (OC (CH ₃ ) ₃ ) ₄

(21.19) Zr (0C ₂ H ₅ ) ₄

(21.20) Zr (OC (CH ₃ ) ₃ ) ₄

(21.21) Ta (OCH ₃ ) Cl ₄

(21.22) Nb (OCH ₃ ) ₄ Cl

(21.23) Ti (OC ₄ Hg) ₄

(21.24) Zr (OCH ₂ CH ₂ Cl) ₄

(21.25) Ta (OCH ₃ ) (OC (CH ₃ ) ₃ ) ₄

(21.26) ζ

Examples of alkali metal hydroxides and alcoholates are;

(22.1) LiOH (22.2) ■ NaOH (22.3) KOH (22.4) LiOCH ₃ (22.5) After ₃ (22.6) NaOC ₂ H ₅

ORIGINAL INSPECTED 509817/1032

(22.7) * NaOC (CH ₃ ) ₃

(22.8) COOK ₃

(22.9) KOC ₂ H ₅

(22.10) KOC (CHo) ο.

In general, the reaction with the alkylene oxide at temperatures ranging from 10 to 160 ⁰ C, preferably 40 to 12O ⁰ C performed. The reaction can be carried out at atmospheric pressure or at elevated pressure. The pressure is preferably 1 to 20 atmospheres or, in particular, 1 to 11 atmospheres. As a rule, the so-called autogenous pressure is used, ie the pressure generated by the reaction mixture itself at the given temperature.

Depending on the intended use of the reaction products, 1 to 50, preferably 5 to 30 mol Alkylene oxide attached to the dye.

It may be useful to carry out the alkoxylation to be carried out in the presence of a second alkylene oxide which does not take part in the actual reaction. For example can be reacted with ethylene oxide and propylene oxide or dioxane as a reaction medium or as a suspension medium use.

The reaction with the alkylene oxide has the advantage that under mild conditions, i.e. at low temperatures

RIGINAL INSPECTED

509817/1032

244A522

and add alkylene oxides directly to an N-methylolated dye compound with a practically neutral catalyst system can. As is known, N-ynethylol compounds are already They are unstable in a weakly acidic medium and form polycondensates or split formaldehyde in a strongly alkaline medium and water off.

After the reaction has ended, it is advisable to neutralize the reaction product with a base. For this alkanolamines such as monoethanolamine, diethanolamine or, in particular, triethanolamine are particularly suitable.

The water-solubilizing glycol ether groups according to the present invention can be used both in the basic dyes as well as in dye precursors by the processes mentioned above.

In the case of the substitution of dye precursors with the polyalkylene radicals mentioned, this follows Manufacturing process one of the usual conversion reactions to the end products. examples for this are inter alia the coupling of diazo compounds with coupling components, with at least one of the starting components one of the defined hydrophilic ether groups should contain.

The new dyes or optical brighteners are suitable for coloring or optical brightening of organic A wide variety of materials, for example for coloring paints, oils, waxes, paper, leather and Furs, but preferably for dyeing or visual enhancement

509817/1032

ORIGINAL INSPECTED

lightening and printing of organic fiber material, in particular textiles. Natural and synthetic fibers can be used as textile fiber material. Examples of natural fibers include: cotton, flax, jute, wool or silk and, as synthetic fibers, regenerated cellulose such as viscose, cellulose ester fibers such as cellulose-2 \ - and cellulose triacet, polyamide fibers, e.g. those made from poly-2-caprolactam (polyamide 6) , Polyhexamethylene diamine adipate (polyamide 6,6), poly-to-amino-undecanoic acid (polyamide 7), polyurethane or polyolefin e.g. polypropylene fibers, linear polyester fibers such as polyethylene glycol terephthalate or poly (1,4-cyclohexane-dimethylol) - terephthalate fibers, polyacrylonitrile fibers or acid-modified polyester or polyamide fibers.

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

These fiber materials can also be used as mixed fabrics with one another or with other fibers, e.g. mixtures made of polyacrylonitrile / polyester, polyamide / polyester, polyester / viscose, polyester / wool and especially polyester / cotton be used.

The fiber material can be present in various processing stages, e.g. in the form of flakes,

509817/1032

Combed sliver, yarn, textured threads, woven fabrics, knitted fabrics, nonwovens or textile floor coverings, such as needle felt carpets, Pile carpets or yarn sheets.

The quantities in which the dyes are in the dye baths can vary within wide limits depending on the desired color depth. In general)! have Quantities of 0.1 to 10 percent by weight, based on the material to be dyed, of one or more dyes have been found to be advantageous.

The dyeing can be done in open or closed systems, e.g. circulation equipment such as cross-winding or tree dyeing machines, reel runners, jet or drum dyeing machines, paddles or jiggers. It will

appropriate /

Material / One constant throughout the entire dyeing process Treated remaining volume in loose form or applied to mechanical devices.

■ Depending on the type of dye used, the fiber material is dyed in acidic, neutral or slightly alkaline Bath, but expediently at a pH of 3 to 7 and preferably 3.5 to 6. The desired pH of the Dyebath is by adding customary pH-influencing Funds discontinued or maintained. 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, and also weak bases such as hexa-

OBIGINAL. INSPECTED

509817/1032

methylene tetramine, or salts with a basic reaction, such as alkali metal acetates, citrates, carbonates, bicarbonates and phosphates. It is advisable to use it as a pH influencing agent Medium buffer mixtures, e.g. 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 be used in the textile industry Contain conventional auxiliaries, e.g. wetting agents, retaining agents, carriers or leveling agents, for example neutral salts such as sodium sulfate or ammonium acetate or - depending on the one used Type of dye - especially non-ionic and cation-active, optionally also anion-active auxiliaries and, under certain circumstances, mixtures of these surface-active agents.

The dye liquor can also contain thickeners. They are used as thickeners in textile printing well-known products, e.g. locust bean gum, galactomannam, Tragacanth, solvitose, polyvinyl alcohol or British gum or the water-soluble salts of alginic acids. But it can also cellulose derivatives, such as methyl cellulose or Find soluble salts of carboxymethyl cellulose use.

509817/1032

At the beginning of the dyeing process, the dye bath advantageously has a temperature of about 40 ^° C .; then the temperature is increased and stained for 15 to 90 minutes, preferably about 60 minutes, at a temperature of about 70 to 100 ⁰ C, preferably at ⁰ C. 95-10O

even/
One can \ .dem by so-called high temperature process in closed vessels under pressure and at temperatures of about 100 ⁰ C, suitably between 110 ° C and 140 ⁰ C color.

The liquor 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 continuously, that is colored by impregnating with practical thickened aqueous dye formulation, "wherein the fixation of the dyes caused by a heat-treatment, for example by steaming at temperatures of 98-105 ⁰ C with neutral saturated steam or heat setting at 180 to 210 ⁰ C. If desired, the impregnated goods can first be dried or stored in a closed vessel at normal or elevated temperature and then steamed at atmospheric pressure or direct pressure.

The new dyes are particularly suitable for printing on the materials mentioned. Man pressure: in usual Manner, if necessary using the usual above-

509817/1032 'owginal

called thickeners on fabrics of animal origin or of vegetable, natural or synthetic origin, on fiber materials made of plastics or glass Wallpaper or paper. If desired, binders made from aldehydes, especially formaldehyde and. Phenols or Products made by condensation of urea, its derivative oil or analogues or aminotriazines with aldehydes, optionally in the presence of monohydric or polyhydric alcohols

are obtained, as well as condensation products of saturated aliphatic dicarboxylic acids and three- or polyhydric alcohols with at least 3 carbon atoms are used in the printing pastes.

The printing itself is done on known ma-

Ro tat ionsdruclcnia gel line machines, such as on a RouleauxdruclcmaschineTVScha-

balloon printing machine or film printing machine. After printing, the material is dried, subjected to a fixing process and then finished by rinsing. The dyes are fixed depending on the fiber type. For example, at 98 ° C to 120 ⁰ C with water vapor with or without pressure, in particular for 20 minutes with saturated steam at 100 ⁰ C or preferably with dry air of about 190 to 210 ⁰ C for 30 to 60 seconds. It is also possible to perform the fixing process with superheated steam for about 5 to 10 minutes at 160 to 200 ⁰ C. 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}

will. 509817/1032 ORIGINAL INSPECTED

^ 444522

The new dyes and optical brighteners can also be transferred to the textile material using a thermal transfer printing process. In this case, if appropriate, thickened color pastes are applied to an auxiliary carrier, for example paper or aluminum foil, for example by spraying in places or over the whole area, coating or, expediently, by printing. After the color pastes have been applied to the inert carrier, they are dried, for example with the aid of a stream of warm air or infrared radiation. Thereafter, the treated support is contacted with the textile material in contact and to 25O ° C, held for so long .100 preferably 180 to 210 ⁰ C, until the applied to the auxiliary support, transferable dyes or optical brighteners are transferred to the textile material. Usually 5 to 60 seconds are sufficient for this.

The action of heat can take place in various known ways, e.g. by passing through a hot one Heating drum, a tunnel-shaped heating zone or by means of a heated roller, advantageously in the presence of a pressure-exerting, unheated or heated counter roll or a hot calender, or by means of a heated plate (Iron or hot press), if necessary under vacuum, produced by steam, oil, infrared radiation or microwaves are preheated to the required temperature or are in a preheated heating chamber.

ORIGINAL INSPECTED

509817/1032

The new dyes and optical brighteners are water soluble. They are distinguished by the fact that they are a group which can be split off under the coloring or lightening conditions contain, which has at least one water-solubilizing radical. Thus, depending on the substrate, both the water-soluble dye according to the invention as well as the The corresponding water-insoluble dye produced therefrom is absorbed onto the fiber material. The inventive pleasure Dyes have the advantage that they have surface-active compounds during dyeing and printing split off, which from the outset has a leveling effect during dyeing and the necessary surface activity for wetting of the fiber surfaces. In most cases is therefore unnecessary when dyeing and printing with the inventive 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 pollution.

In the following examples, the present invention is further illustrated, but without referring to the Limit the scope of the examples. The percentages are percentages by weight.

ORlGSMAL INSPECTED

509817/1032

example 1

a) 25 g of a copper phthalocyanine dye

formula

CuPc

are suspended in 200 ml of ethanol and 25 g of paraformaldehyde offset. The mixture is then adjusted to a pH of 10 to 12 with triethanolamine and left

they react ^{at 60 °} C. for 5 hours. The reaction mixture is then adjusted to pH 7 with glacial acetic acid. The methylolated dye compound is removed by evaporation at 40 to 60 ⁰ C under a reduced pressure of 11 mm Hg by the excess formaldehyde and the solvent, and getx'ocknet at 40 ⁰ C in vacuo. 34 g of a resinous methylolated dye compound are obtained. Instead of triethanolamine, triethylamine or sodium hydroxide can also be used as the basic catalyst. ...

ORIGINAL MSPECTED 509817/1032

b) 9.0 g (0.01 mol) of the according to a) methylolated dye are melted with 4.4 g (0, l mol) of ethylene oxide and 100 mg of Ta (OC ₉ Hc) ₉ i ⁿ a glass tube. At a pressure of 8 atli and with shaking in a thermo stabilized oil bath at 8O ⁰ C, the reaction mixture is allowed to react for 16 hours. 13.2 g of a water-soluble phthalocyanine dye of the formula are obtained

/ (SO ₃ H)
CuPc ^

'SO ₉ NH-CH ₉ O ^ CH ₉ CH ₉ O) H

ι Η

> H ζ

x + y + z = 10

Yield 89% of theory.

The following table contains further according to the invention water-soluble dyes, which can be obtained when using the embodiments described in Example 1 under a) and b) obtained by first methylolating the dyes in column 2 and the corresponding N-methylol compounds at the temperatures indicated in column 5 with the alkylene oxides of column 3, in the presence of the catalysts of Column 4 implements. In column 6 of the table, the yields obtained for the new dyes are given in g and percent by weight given the theory.

50981 7/1032

1 2 G Mole 3 Mole 4th 5 6th % example dye 6.34 0.05 Ethylene oxide 0.1 0.1g Kata ⁰ C yield 95 No. Formula No. 5.0 0.01 G 0.2 lyser G 80 2 LX 5.0 0.01 4.4 0.25 Ta (OC ₂ H ₅ ) 3 80 10.2 80 3 XXXVIII 5.0 0.01 8.8 0.3 Ta (OC ₂ H ₅ ) 3 80 11.5 80 4th XXXVIII 8.5 0.01 11.0 0.25 Ta (OC ₂ H ₅ ) ₅ 80 15.8 98 5 XXXVIII 8.5 0.01 13.2 0.3 Ta (OC ₂ H ₅ ) 3 80 18.3 98 6th IXL 8.5 0.01 11.0 0.2 Ta (OC ₂ H ₅ ) ₅ 80 20.0 92 7th IXL 16.0 0.015 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 22.0 99 8th XXVIII 7.14 0.05 8.8 0.2 Ta (OC ₂ H ₅ ) 3. 80 16.2 89 9 XXVIII 7.14 -0.05 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 29.0 99 10 XL 7.14 0.05 8.8 0.35 Ta (OC ₂ H ₅ ) ₅ 80 14.2 99 11 XL 9.0 0.01 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 20.2 97 12th XL 9.0 0.01 15.4 0.4 Ta (OC ₂ H ₅ ) ₅ 80 22.5 98 13th XLI 9.0 0.01 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 22.0 97 14th XLI 9.0 0.01 17.6 0.4 Ta (OC ₂ H ₅ ) ₅ 80 26.2 97 15th XLI 9.6 0.005 13.2 0.3 Zr (OC ₂ H ₄ Cl) ₄ 80 21.6 99 16 XLI 9.6 0.005 17.6 0.4 Zr (OC ₂ H ₄ Cl) ₄ 80 26.0 99 17th XXVI 9.0 0.005 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 22.9 98 18th XXVI 10.0 0.005 17.6 0.25 Ta (OC ₂ H ₅ ) 3 80 27.0 99 19th XXXVII 10.0 0.005 13.2 0.12 Ta (OC ₂ H ₅ ) ₅ 80 22.0 99 20th XXXVII 4.8 0.005 11.0 0.2 Ta (OC ₂ H ₅ ) ₅ 70 20.0 85 21 XXXVII 4.5 0.005 5.0 0.2 Ta (OC ₂ H ₅ ) ₅ 70 15.0 97 22nd XLI 7.25 0.01 8.8 0.25 Ta (OC ₂ H ₅ ) ₅ 80 13.0 98 23 XLI 9.0 0.01 8.8 0.2 Zr (OC ₂ H ₄ Cl) ₄ 80 13.1 99 24 LVIII 8.0 0.01 11.0 0.325 Ta (OC ₂ H ₅ ) ₅ 80 18.0 99 25th XLI 7.25 0.01 8.8 0.15 Ta (OC ₂ H ₅ ) ₅ 80 17.8 96 26th XXXV 7.25 0.01 15.0 0.25 Ta (OC ₂ H ₅ ) ₅ 70 23.0 98 27 LVIII 9.6 0.012 6.6 0.3 Ta (OC ₂ H ₅ ) ₅ 70 13.5 99 28 LVIII 8.0 0.01 11.0 0.15 Ta (OC ₂ H ₅ ) ₅ 70 18.0 94 29 XXXV 8.0 0.01 13.2 0.25 Ta (OC ₂ H ₅ ) ₅ 50 23.0 96 30th XXXIV 8.6 0.02 6.6 0.2 Ta (OC ₂ H ₅ ) ₅ 70 13.8 89 31 XXXIV 8.6 0.02 11.0 0.25 Ta (OC ₂ H ₅ ) ₅ 70 18.5 97 32 L. 8.8 Ta (OC ₂ H ₅ ) ₅ 80 15.5 33 L. 11.0 Ta (OC ₂ H ₅ ) ₅ 80 19.2

509817/1032

OWGINAL INSPECTED

: G Mole j Mole 4th j! 44 452; % 1 4.3 0.01 0.2 0.1g Kata 5 90 example 2 8.9 0.02 0.2 lyser ° c 6th 96 No. dye 8.9 0.02 Ae thy1enoxide 0.25 Ta (OC ₂ H ₅ ) ₅ yield 99 34 Formula No. 8.9 0.02 G 0.35 Ta (OC ₂ H ₅ ) ₅ 80 G 98 35 L. 17.8. 0.04 8.8 0.3 Ta (OC ₂ H ₅ ) ₅ 80 11.8 96 36 XXXIII 13.35 0.03 8.8 0.3 Ta (OC ₂ H ₅ ) ₅ 80 17.0 97 37 XXXIII 6.33 0.015 11.0 0.15 Ta (OC ₂ H ₅ ) ₅ 80 20.0 95 38 XXXIII 6.33 0.15 15.4 0.3 Ta (OC ₂ H ₅ ) ₅ 80 24 98 39 XXXIII 8.44 0.02 13.2 0.15 Ta (OC ₂ H ₅ ) ₅ 80 30th 99 40 XXXIII 8.44 0.02 13.2 0.1 Ta (OC ₂ H ₅ ) ₅ 80 26th 94 41 IX 7.26 0.015 6.6 0.15 Ta (OC ₂ H ₅ ) ₅ 80 12.4 94 42 IX 7.26 0.015 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 19.2 97 43 IX 9.68 0.02 6.6 0.15 Ta (OC ₂ H ₅ ) ₅ 80 15.0 98 44 IX 9.48 0.02 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 12.2 96 45 VIII 9.48 0.02 6.6 0.15 Ta (OC ₂ H ₅ ) ₅ 80 13.2 95 46 VIII 7.11 0.015 13.2 0.15 Ta (OC ₂ H ₅ ) ₅ 80 20.0 96 47 VIII 7.11 0.015 6.6 0.3 Ta (OC ₂ H ₅ ) 3 80 16.0 98 48 XXXI 6.52 0.015 4.4 0.125 Ta (OC ₂ H ₅ ) ₅ 80 13.5 96 49 XXXI 6.52 0.015 6.6 0.125 Ta (OC ₂ H ₅ ) ₅ 80 15.5 94 50 XXXI 6.52 0.015 6.6 0.125 Ta (OC ₂ H ₅ ) 3 80 13.3 98 51 XXXI 8.9 0.02 13 _} 2 0.1 Nb (OC ₂ H ₅ ) ₅ 80 20th 98 52 XXXIII 7.45 0.02 5.0 0.2 Zr (OC ₂ H ₄ Cl) ₄ 80 11.2 97 53 XXXIII 7.45 0.02 5.0 0.1 Ta (OC ₂ H ₅ ) ₅ 80 11.0 96 54 XXXIII 9.0 0.03 5.0 0.15 Ta (OC ₂ H ₅ ) ₅ 80 11.4 96 55 XXXIII 9.0 0.03 4.4 0.3 Ta (OC ₂ H ₅ ) ₅ 50 13.0 98 56 XCI 5.58 0.01 8.8 0.1 Ta (OC ₂ H ₅ ) ₅ 50 15.0 89.8 57 XCI 5.58 0.01 4.4 0.2 Ta (OC ₂ H ₅ ) ₅ 80 11.5 98 58 I. 8.38 0.015 6.6 0.3 Ta (OC ₂ H ₅ ) 3 80 15th 96 59 I. 11.16 0 _s 02 13.2 0.2 Ta (OC ₂ H ₅ ) ₅ 80 22nd 96 60 XXXII 5.5 0.02 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 9.7 99 61 XXXII 5.5 0.02 "8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 14.2 93 62 XXXII 5.5 0.02 13.2 0.3 Ta (OC ₂ H ₅ ) ₅ 80 21 98 63 XXXII 8.8 Ta (OC ₂ H ₅ ) ₅ 80 19.3 64 XIII 4.4 Ta (OC ₂ H ₅ ) ₅ 80 10.3 65 XIII 8.8 80 13.5 XIII 13.2 18.5

509817/1032

ORIGINAL INSPECTED

- 55 table

1 2 G Mole 3 Mole 4th 5 6th % example dye 4.51 0.01 Ethylene oxide 0.1 0.1 g kata ⁰ C 98 No. Formula No. 4.51 0.01 G 0.15 lyser yield 98 66 XII 4.51 0.01 4.4 0.2 Ta (OC ₂ H ₅ ) ₅ 80 G 96 67 XII 5.83 0.01 6.6 0.15 Ta (OC ₂ H ₅ ) ₅ 80 8.9 96 68 XII 5.83 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 11.0 98 69 XIV 5.83 0.01 6.6 0.3 Ta (OC ₂ H ₅ ) ₅ 80 13.0 86 70 XIV 5.11 0.01 8.8 0.1 Ta (OC ₂ H ₅ ) ₅ 80 12.0 95 71 XIV 5.11 0.01 13.2 0.2 Φα (C \ C H ^
X Cl ^ UU ryil q ) - 80 14.5 97 72 LI 4.52 0.01 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ '80 16.5 99 73 LI 4.52 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 9.2 97 74 XV 4.33 0.01 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 13.6 96 75 XV 4.33 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80- 9.0 98 76 XXX 4.3 0.01 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 13.0 99 77 XXX 4.3 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 8.5 98 78 VII 6.8 0.02 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ . 80 13.0 97 79 VII 6.8 0.02 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 .9.0 95 80 XVIII 9.1 0.02 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 13.0 97 81 XVIII 9.1 0.02 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 11.0 97 82 XIX 7.1 0.02 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 15th 96 83 XIX 7.1 0.02 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 . 13.2 97 84 XII 8.8 0.01 4.4 0.1 Ta (OC ₂ H ₅ ) ₅ 80 17.6 99 85 XII 8.8 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 11.2 99 86 XX 9.9 0.01 4.4 0.15 Ta (OC ₂ H ₅ ) ₅ 80 15.6 99 87 XX 9.9 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 13.2 98 88 XXI 8.36 0.01 6.6 0.04 Ta (OC ₂ H ₅ ) ₅ 80 17.6 91 89 XXI 8.36 0.01 8.8 0.08 Ta (OC ₂ H ₅ ) ₅ 80 16.5 97 90 XXII 12.0 0.04 1.76 0.2 Ta (OC ₂ H ₅ ) ₅ 80 18.5 98 91 XXII 6.0 0.02 3.52 0.2 Ta (OC ₂ H ₅ ) ₅ 80 9.3 93 92 LXXX 6.0 0.01 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 11.6 97 93 LXXX 10.0 0.014 8.8 0.2 Ta (OC ₂ H ₅ ) ₅ 80 20.5 99 94 LXXXI 4.29 0.01 8.8 0.1 Ta (OC ₂ H ₅ ) ₅ 80 14th 97 95 LXXXI 4.29 0.01 8.8 0.2 Ta (OC ₂ H) ₅ 80 14.5 98 96 LXX 4.4 Ta (OC ₂ H ₅ ) ₅ 80 18.8 97 LXX 8.8 Ta (OC ₂ H ₅ ) ₅ 80 8.6 13.0

509817/1032

OMGlNAL INSPECTED

Example 98

a) 30 g of the 1: 2 chromium complex of a dye formula

Cl

SO ₂ NH ₂

are dissolved in 200 ml of ethanol and treated with 30 g of paraformaldehyde. The mixture is adjusted to a pH of 10 with triethanolamine and allowed to react ^{at 60 ° C. for 5 hours.} The reaction mixture is then adjusted to pH 7 with 3 ml of glacial acetic acid. The methylolated dye compound is removed by evaporation at 40 to 60 ⁰ C under reduced pressure of 11 mm Hg from the excess formaldehyde and the solvent, and at 40 ⁰ C in vacuum overnight. 55 g of a resinous, dimethylolated dye compound are obtained.

b) 9.9 g (0.01 mol) of the dye methylolated according to a) are mixed with a mixture of 5.8 g (0.1 mol) propylene oxide and 4.4 g (0.1 mol) ethylene oxide and 100 mg of a catalyst mixture of KOC ₂ H ₅ and Ta [OC (CHo) - J ₅ in a weight ratio of 1: 1 melted in a glass tube.

ORIGINAL INSPECTED

509817/1032

This mixture is reacted at a pressure of 5.3 atli with shaking in a thermostatically controlled oil bath at 90 ⁰ C for 16 hours for reaction. 18.9 g of a water-soluble dye of the formula are obtained

> so \ LJ Cl
I. Il so ₂ 0-CH " j C-. O'
I. Cl
I. Cl % / T
Cl I-n = nLJ ^> 1-N = N-T ^ S

,. = io

Yield 89% of theory.

Example 99

9.9 g (0.01 mol) of the dye methylated according to Example 98 a) are in a glass tube with 100 g of a catalyst mixture of KOC2HC and Ta (OC2H, -), - in a ratio of 1: 1 and with a mixture of 11 , 6 g propylene oxide and 1 g ethylene oxide melted down. This mixture is placed in a thermostated oil bath at 90 ⁰ C for 16 hours for reaction. 17 g of a viscous dye are obtained. Yield 75% of theory.

509817/1032

ORIGINAL INSPECTED

i8 -

Application examples

Example 101

1.5 g of the dye obtained in Example 61 are dissolved in 2000 g of water in a printing dyeing machine. The solution is adjusted with sek.Natriumeitrat and hydrochloric acid to a pH value of 3, heated to 70 ⁰ C. Then 50 g of polyethylene glycol terephthalate fabric are introduced. The bath is heated in the closed apparatus to 130 ^° C. in 30 minutes and dyed under pressure at this temperature for 60 minutes. The coloration obtained is then rinsed with water and dried. After the usual hydrosulphite cleaning, a color is obtained in a well-developed orange shade, degree of drawing 96 ⁰ L.

Example 102

In a dye liquor, the .0.3 g of the dye obtained according to Example 61, 0.2 ml of 85 / o formic acid and 0.2 g of a mixture consisting of 0.152 g of a 45% aqueous solution of the disodium salt of dodecyl diphenyl ether disulfonic acid, 0.015 g of a compound of the formula

«3PSCTED

509817/1032

CH

^C 18 ^H 35

CH ₀ -CH-O (CH ₀ CH ₀ O) H λ ι. ζζρ

η + ρ = 18

CH ₃ SO ₄

and contains 0.033 g of water, one enters at 40 ⁰ C with 10 g of polyamide. 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

A fabric consisting of bleached and merceri-

Cotton with a weight of 120 g / m is printed with a roller printing paste, which is prepared in the following way:

450 g of a 5% aqueous sodium alginate solution are mixed with
440 g of water diluted and

30 g diammonophosphate 1: 2 added.

This solution is adjusted to a pH of 8 with triethanolamine and mixed with 80 g of the dye prepared according to Example 19 with stirring.

After drying, the printed fabric becomes a

509817/103 2

ORIGINAL INSPECTED

-ίο

Treatment in dry air at 200 ^° C. for 60 seconds and then ^{soaped cold at 60 °} C. with 0.5 g / l of a nonionic ethylene oxide product. 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 viscose cellulose fabric instead of the cotton fabric is also obtained a print of an intense pure golden yellow hue.

Example 105

The procedure is as described in Example 103, but using a fabric made of polyethylene glycol terephthalate fibers instead of cotton, a print of an intense golden yellow color is also obtained.

Example 10.6

• Following the procedure as described in Example 103, but using a fabric of polyacrylonitrile fibers instead of cotton under steaming at 100 ⁰ C for 20 minutes instead of the treatment in dry air at 200 ° .C, the result is an intensely golden yellow print.

ORIGINAL mi ?? - ' 509817/1032

Example 107

Proceed as described in example 108, however using a wool fabric instead of one made of polyacrylonitrile one also obtains one An intense golden yellow print.

Example 108

The procedure is as described in Examples 103 to 107, each using an example according to the present invention produced dye instead of the dye described there, corresponding prints are obtained in a good developed red hue.

Example 109

If one proceeds as described in Examples 103 to 107, in each case using one according to Example 10

produced dye instead of the dye described there, corresponding prints are obtained in a good developed lemon yellow hue.

Example 110 ''

A bleached and mercerized cotton fabric

of 140 g / m weight is printed in film printing with a monochrome design using a printing paste, which on

509817/1032 original

- 62 - .λ ι, ι ι ρ / - ο

j: 4 4 4 b ά 2

is made in the following way.

80 g of a dye prepared according to Example 44

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 cloth is fixed for 1 minute at 200 ⁰ G in dry hot air and then cold, then soaped at 6O ⁰ C using 2 g / l soap and then rinsed again cold. A print of a well developed brown shade is obtained.

Proceed as described in Example-110, however using a fabric made of viscose or polyethylene glycol terephthalate instead of cotton, corresponding prints are also obtained from a well-developed one brown hue.

Example 112

If you proceed. as described in example 110, but using a fabric made of polyamide, wool or polyacrylonitrile instead of cotton and steaming at 100 ^° C. for 20 minutes instead of fixing in hot air at 200 ^° C., corresponding prints are also obtained

509817/10 3 2 ORlGiNAL INSPSC

" ^ό3 ". -L'444522

of a well developed brown hue.

Example 113

With 10 g of a multi-fiber tape No. 7-6205 goes into a dye liquor of 40 ⁰ C in the liquor ratio 1:40

3 % of one prepared according to Example 49.

Dye

Contains 4% diarnmon phosphate.

Then it heats the fleet 25 minutes at 95 ⁰ G 'and stained for 1 hour at this temperature. After the liquor has cooled down, it is rinsed and dried. A red color is obtained.

Example 114

Multi-fiber tape No. 7-6205 with an Imp 3: Ugnier liquor containing 0.3 g / l of a dye prepared according to Example 49, 0.2 g / l diammonophosphate, 0.02 g / l of a nonionic ethylene oxide product, at 20 to 30 ^° C., then squeezed to 100% based on the dry weight of the product, dried at 80 ⁰ C for 10 minutes and then fixed at 19O ⁰ C for 1 minute. The dyeing is washed cold, then at 50 ^° C. and again cold and dried. A red color is obtained. The present multi-fiber tape consists of cotton, cellulose, silk, nylon, polyacrylonitrile, modacrylic (Dynel), polyethylene glycol terephthalate, cellulose triacetate and cellulose acetate. The base fabric is wool.

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ORIGINAL lf * 4SPECTED

Example 115

A cotton fabric weighing 120 g / m, bleached

and causticized with a printing paste of the following composition printed:

910 g of an aqueous 2.5% sodium alginate

solution will be with

10 g ammonium chloride mixed with ammonia

set to pH 8. 80 g of the according to example are added to this paste 59 obtained dye was added. After printing, it is dried, fixed and washed out as indicated in Example 103. A print of a well developed brown tone is obtained. '. "

Example 116

The procedure is as indicated in Example 115, but using a fabric made of viscose or polyethylene glycol terephthalate instead of cotton, corresponding prints are obtained in a well-developed brown Volume.

Example 117 ''.

The procedure is as indicated in Example 1.15, but using a fabric made of polyamide 6,6, polyacrylonitrile or wool instead of cotton and with steaming

■ ORIGINAL INSFCCT

5098 17./1032

^ 4.44522

at 10O ⁰ C for 20 minutes instead of fixing in hot air at 200 ⁰ C, it is also appropriate prints as receives from a well-developed brown tone.

Example 118

The procedure is as indicated in Examples 115-117, but using a printing paste consisting of 920 g of 1.5% aqueous sodium alginate solution and 80 g of des of the dye obtained according to Example 59, brown prints of equal size are likewise obtained.

If one proceeds as indicated in Examples 115-118, but using the same amount of according to Example 89 of the dye obtained, corresponding prints of a well-developed blue tone are also obtained.

In game 120

Mercerized cotton fabric is impregnated on a padder at 40 ^° C. with a liquor of the following composition:

40 g / l of the dye obtained according to Example 61, 100 g / l of 2.5% strength aqueous sodium alginate solution and

2 g / l dibutyl naphthalenesulfonic acid sodium salt and 85% formic acid to achieve a pH value of 2.8. That

509817/10 3 2 original inspected

to about 100% of the product weight squeezed fabric 2 minutes, dried at 100 ⁰ C and then for
Fixed at 210 ° C for 90 seconds. The dyed goods are made with
Rinsed with water, soaped and dried. You get one
strong orange color.

If one proceeds as indicated in Example 120, used however, a mixed fabric made of polyethylene glycol terephthalate and cotton (33:66) also gives an orangs Coloring.

ORIGINAL

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Example 121

A fabric consisting of bleached and merce-

rised cotton of 120 g / m is stenciled printed with a printing paste, which is prepared in the following way:

25 g of a sodium alginate compound are introduced into 760 g of water with vigorous stirring. After that will be in the resulting pulp, always with vigorous stirring, first 100 g of the dye prepared according to Example 50, then 100 g of a partially etherified melamine-formaldehyde precondensate and 15 g of a 2-amino-2-methylpropanol hydrochloride compound added.

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 122

If one proceeds as described in example 121, but using a fabric made of polyethylene glycol terephthalate fibers instead of cotton, a print of an intense red color is also obtained.

ORIGINAL INSPECTED

5 09817/1032

Example 123

The procedure is as described in Example 121, but using a mixed fabric made of polyethylene glycol terephthalate and cotton (1: 2) instead of the cotton alone, you also get a print of one intense red hue.

Example l 124

If one proceeds as described in Examples 121 to 123, in each case using one according to the example 61 produced dye, corresponding prints are obtained in an intense yellow-brown shade.,

Example 125

If one proceeds as described in Examples 121 to 123, in each case using one according to the example produced dye, corresponding prints are obtained in an intense red-brown shade.

Example 126

100 g of the dye prepared according to Example 61 are mixed in 900 g of a paste by stirring, which is prepared in the following way:

25 g of sodium alginate powder are added by slowly sprinkling into 925 g of water and using a High-speed stirrer to a viscosity of the preparation of

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Brought 10,000 cP. Then 50 g of a high-boiling gasoline fraction - hineinemulgiert (bp 120 180 ⁰ C).

In the screen printing process, a weakly sized paper with a basis weight of 70 g / nr is made with the above Printing ink paste printed. The printed paper is dried at room temperature. On the paper carrier treated in this way a fabric made of polyethylene glycol terephthalate is placed,

whereupon the carrier and fabric are brought into contact ^{at 210 °} C. for 30 seconds by means of a heating plate. 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.

Example 127

If you proceed as described in example 126,
however, using the dye prepared according to Example 50, the transfer printing process gives a strongly colored red print which is also good wetfast.

INSPECTED

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Claims (8)

Claims 1. Water-soluble organic dyes and optical brighteners, characterized in that they contain at least one hydrophilic ether groups derived from polyols which have the general structure - CH ₂ - 0 - is bound to the dye or «brightener skeleton, the nitrogen to an acid amide grouping of the dye or brightener molecule belongs and the oxygen to the hydrophilic ether residue is bound. 2. Organic dyes and optical brighteners according to Claim 1, characterized in that it contains at least one nonionic, water-soluble group of the formula - X _n - N - CHo - 0 - Z in the -X, -N- one. Represents acid amide residue, which via X, or N is connected to the dye or brightener skeleton or is part of such, X-, the divalent bridge -CO-, CS, -C = NH or -SO ₀ - or a carbon atom, the 509817/1 032 ^ 444522 Part of a nitrogen heterocycle and adjacent to the ring nitrogen, Z is an optionally substituted one Mono- or polyalkylene glycol radical with an average molecular weight of at most 2500 mean. 3. Organic dyes according to claim 2, characterized marked that they are of the formula FfXj - N - CH ₂ - 0 - Z 'R ^/ correspond, in which F is the radical of an organic dye, X ₁ -N- is an acid amide radical, R is hydrogen or an organic The remainder, η is 1 to 6 and X. and Z are those specified in claim 2 Have meaning. 4. Organic dyes according to claim 2, characterized in that they have the formula Ff N -CH ₂ -OZ correspond, wherein F and Z have the meaning given in claim 3, X ₂ the -CO- or -SO ₂ bridge and R, an optionally substituted and / or via an oxygen 509817/10 3 2 ORIGINAL INSPECTED atom or an amino group bonded hydrocarbon residue and n are 1 to 3. 5. Process for the production of organic dyes or optical brighteners, characterized in that that one dyes, optical brighteners or dye precursors which have at least one free to an amide nitrogen have bonded methylol grouping, with an 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 alkali metal, alkoholates converts, and in the case of the use of dye precursors this is completed by reaction with the other dye component to give the corresponding final dyes. 6. The method according to claim S _5, characterized in that that one alkylene oxides of the formula CH - R ₇ where Ry is hydrogen, alkyl having 1 to 3 carbon atoms, phenyl or a CH ₀ - CH ₉ - O radical is used. ORIGINAL INSPECTED 509817/1032 7. The method according to any one of claims 5 and 6, characterized in that the reaction is carried out in the presence of a metal alcoholate of the formula Me (O-Ak) _r (R ₈ ) _q _ _r where Me is a q-valent transition metal of groups IY, V or VI of the periodic table, Ak alkyl with 1 to 4 carbon atoms, haloalkyl with 2 to 4 carbon atoms, Phenyl, benzyl or cycloalkyl with a maximum of 12 ring carbon atoms, Rg halogen or alkoxy with 1 to 4 carbon atoms, r 1 to q and q 4, 5 or 6 are carried out. 8. The method according to any one of claims 5 to 7, characterized in that the reaction in the presence of a Metal alcoholates of the formula Me ₂ (OAk ₁ ) where Me is zirconium, niobium, tantalum or VJoIfram, Ak ₁ alkyl with 1 to 4 carbon atoms or haloalkyl with 2 to 4 carbon atoms and q ₁ 4, 5 or 6 according to the valency of the metal mean performing ". ORIGINAL INSPECTED 509817/1032