DE1568258A1 - Use of amphoteric polyglycol compounds as leveling agents - Google Patents

Description

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CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND

Case 565I / I + 2 / E

GERMANY

Use of amphoteric polyglycol compounds as

Leveling agent.

The present invention is the

Use of amphoteric polyglycol compounds as leveling agents when dyeing nitrogen-containing dyes with acidic dyes dyeable fibers. These compounds are amphoteric derivatives of

a) a nitrogen-bonded aliphatic hydrocarbon radical with 12 to 2h carbon atoms and -. ■ · «

SAD ORIGINM. 009815/1666

b) - (CH ₂ -CH ₂ -O -) groups bound to nitrogen, where k is a whole positive number and a total of 4 to 12 -CHp-CHp-O groups are present in the molecule,

containing'Polyglykolverbindungen which

on the one hand quaternized with organic halogen compounds

and on the other hand with at least dibasic oxygen acids with the formation of acidic ester groups are esterified.

These amphoteric polyglycol compounds are conveniently prepared by adding polyglycol compounds which

α) a nitrogen-bonded aliphatic hydrocarbon with 12 to 24 carbon atoms,

β) (-CHp-CH ₂ -O) -H groups bonded to nitrogen, where k is a positive integer and a total of 4 to 12 -CHp-CHp-O groups are present in the molecule, and

7) exclusively tertiary amino groups

contain, on the one hand quaternized with organic halogen compounds and on the other hand at at least one -CHp-CHp-OH group esterified to acidic esters derived from an at least dibasic oxygen acid.

The polyglycol compounds preferably contain up to 9 -CHp-CHg-O groups (ethenoxy groups). Furthermore do they contain saturated or unsaturated aliphatic ions

Hydrocarbon radicals that are branched or preferably un-

009815/1666

BATH ORIGINAL

are branched and advantageously 16 to 18 carbon atoms exhibit. The quaternization and the esterification can be carried out in can be executed in any order. The -CHg-CHp-OH Groups become with functional derivatives of di- or polybasic oxo acids under such conditions esterified that at least one acidic ester group, preferably introduced in the form of an alkali, ammonium or amine salt will"

A preferred subgroup of the polyglycol derivatives, which are particularly easy to access are distinguished from organic halogen-containing quaternizing agents and from acidic esters of the formula

(D

R-

-N-

-N

derivative quaternary compounds. In this formula, R is a preferably unbranched aliphatic hydrocarbon radical with 12 to 2k carbon atoms, X is the radical formed by separating an HO group from a polybasic organic or inorganic acidic acid, this radical preferably being in the form of alkali, ammonium - or amine salsa is present ,, m the number O or 1, P _ "._. _t

00 9815/1666 ^ _BAD original

the number 2 or Z> » s an integer with a value of at least 1 and at most 2 + m and p, q, and r integers, the sum ρ + q + r being 4 to 12 and preferably 6 to 9. The amphoteric polyglycol compounds of the formula (I) can be obtained by adding nitrogen-containing polyglycol compounds of the formula

-N fCI

2 'n

-H

-N

-ta

wherein R, n, m, p, q and r have the same meaning as in formula (I), quaternized in any order on the one hand with organic halogen compounds and on the other hand on at least one -CH ₂ -CH ₂ -OH- group to one another esterified acidic esters derived from at least dibasic oxygen acid, the reaction conditions preferably being selected such that the acidic ester groups are introduced in the form of their alkali, ammonium or amine salts.

As starting materials for the production of the invention Polyglycol compounds to be used that are both acidic Containing ester groups and quaternary ammonium groups are suitable particularly good basic polyglycol ethers of the formula

009815/1666

BATH. ORIGINAL

(III) R N

(HO) - H

where R is a preferably unbranched aliphatic hydrocarbon radical having 12 to 2k, preferably 16 to 20 carbon atoms and ρ and q are whole numbers, the sum ρ + q k being up to 12 and preferably 6 to 9.

Examples of compounds of the formula (III) are: the reaction product of 1 mole of dodecylamine with about 6 moles of ethylene oxide, the reaction product of 1 mole of oleylamine with 6, 8 or 12 moles of ethylene oxide and the reaction product of 1 mole of palmityl, stearyl, arachidyl - Or behenylamine with 4, 8 or 12 moles of ethylene oxide, and the reaction products of mixtures of such amines with 4 to 12 moles of ethylene oxide per mole of amine mixture.

Furthermore, polyglycol compounds are also particularly suitable the formula

(IV) R * -f-OH ₂ - * 5 H

(-CH ₂ -CH ₂ -

- (- CH ₂ -OH ₂ -

wherein R is a preferably unbranched aliphatic hydrocarbon radical with IS up to 2k, preferably 16 to 18

009815/1666

Carbon atoms, η the number 2 or 3 and p, q and r denote integers, the sum p + q + r being 4 to 12, preferably 6 to 9.

Examples of compounds of the formula (IV) that may be mentioned are:

The reaction product of monoalkylpropylenediamine, the alkyl radical of which corresponds to the remainder of the tallow fatty acids, with 8 moles of ethylene oxide; the reaction product of monoalkylpropylenediamine, the alkyl radical of which is unbranched and 16 to Contains l8 carbon atoms, and 6 moles of ethylene oxide.

Both the quaternization and the esterification are advantageously carried out by known methods, with no separation is necessary.

Conventional halogen-containing alkylating or aralkylating agents, such as ethyl bromide, can be used for the quaternization or benzyl chloride can be used; however, chloroacetamide, ethylene chlorohydrin are preferred as quenching agents, Ethylene bromohydrin, epichlorohydrin or epibromohydrin, because they are used in dyeing auxiliaries with particularly good properties, especially as leveling agents for dyeing unwoven wool with wool dyes contained in acidic groups.

As polybasic acids oxygen for the formation of the acid esters may organic polycarboxylic acids, trie a, fi. Succinic sulfonaHurt or polybasic «inorganic

009815/1666 && original

Oxygen acids, such as sulfuric acid, are used. Instead of the acids, their functional derivatives such as acid anhydrides, acid halides, acid esters or acid amides can be used. According to a particularly preferred embodiment, the acid sulfuric acid esters are prepared directly in the form of their ammonium salts by heating the starting materials with amidosulfonic acid in the presence of urea. Both the quaternization and the partial esterification conveniently be carried out by simply mixing the reactants with heating, conveniently to a temperature between 50 ° and 100 ⁰ C.

The resulting polyglycol compounds to be used according to the invention, both the quaternary ammonium groups as well as acidic ester groups or acidic ester groups in salt form, are readily water-soluble compounds with pronounced amphoteric character.

As already mentioned above, the poly-

glycol ether derivatives valuable technical properties as a leveling agent for dyeing nitrogen-containing fibers, in particular WoIIe ₅ containing with acidic water-solubilizing groups wool dyes, specifically Reactivates "" = materials and lsi Metallkomplerfärbstoffen · While it is already different types of amino-containing Polyglykolätherderivaten for this purpose are voi -has been suggested "wio Ii -.- for example, by addition: δ * 1 -6 to JO mol Aethylsr.-

0098 1 S / 16SS - - - - *

BATH ORIGINAL

oxide of higher molecular weight, primary, aliphatic monoamines, such as oleylamine, basic polyglycol compounds obtained. These known leveling agents, which as usual in amounts of about 0.1 to 8 percent by weight, advantageously in amounts of 0.5 to 3 percent by weight, based on the amount by weight of the material to be dyed but are not capable of general application to wool. While when using leveling agents very level dyeings of the specified type can be obtained under ideal apparatus conditions when dyeing under the most unfavorable apparatus conditions, so with wool top, especially when dyeing wool yarn in Apparatus according to the so-called hanging system, with wool dyes in the presence of the mentioned leveling agents, usually different disturbing effects. In addition to the annoying appearance of visible foam, air bubbles also become very persistent held on the fiber surface, whereby the even penetration of the dyed material is disturbed and that Material has a tendency to rise to the surface of the bath. This has a special effect when dyeing cross-wound bobbins in a deformation of the material.

Furthermore, the known leveling agents also increase the adhesion of the individual fibers to one another, so that a more or less strong sticking of the yarns occurs, which leads to channel formation in the dyed material and thus to unevenness leads. The known leveling agents also have the

0 0 9 8 15/1666 -X-, - ♦ -

BATHROOM OBIGINAL

disadvantageous property that addition compounds result from

mostly such / dye and leveling agent when heated / below the boiling temperature due to dehydration in droplets (so-called "cloud point") which are held mechanically by the material. This phenomenon, which is referred to as “syrup formation ¹¹ (English“ draining effect ”), can lead to dyeings which are not resistant to rubbing and which are uneven.

It has been proposed to eliminate these disadvantageous properties of the known leveling agents by adding them to remove special combination products such as mixtures of paraffin oil, emulsifiers and defoamers. The use of such preparations, however, makes the dyeing process complicated and expensive.

Finally, it is also known to use compounds as wool leveling agents which are obtained by reacting on esterifiable polyglycol compounds which contain at least one basic nitrogen atom, a lipophilic radical and a polyglycol chain of at least 4 ethoxy groups in the molecule. Lets sulfating or phosphating agents act and quaternizes at least one tertiary nitrogen atom with dimethyl sulfate. The known compounds of this composition but are of limited use as leveling agents for wool dyes and effect in addition to the deformation of cross-coil "

Surprisingly, show the erfindungsgeißäas to ■ Denden-polyglycol no ä®v eraäfenten

0098 15 / 1.666 _BAD origina

parts of the well-known leveling agents used in dyeing, _

Wool, so that for the first time leveling agents were created for the Wm Purpose W * , which were added to the dye bath alone,
Satisfy all practical requirements and thus make the use of auxiliary preparations, which complicate and make the staining process more expensive, superfluous for the first time.

The present invention accordingly also provides a process for dyeing nitrogen-containing, Fibers that can be dyed with acidic dyes, in particular

Wool, whereby these fibers in an aqueous medium with dyes, the water-solubilizing, acidic groups, in particular contain sulfonic acid groups, in the presence of the new, amphoteric polyglycol ether compounds defined at the outset treated as a leveling agent.

According to the dyeing process according to the invention, those nitrogen-containing fibers can be dyed which. can be dyed in the usual way with acidic dyes , for example silk, polyamide fibers made from € -caprolactam or such
from adipic acid and hexamethylenediamine. The process has proven to be particularly advantageous when dyeing

Wool, possibly mixed with other nitrogenous or nitrogen-free fibers.

The wool yarn is dyed with wool dyes using the dyeing methods customary for wool. There come customary wool dyes can be used for this purpose, which

"Ine sour waaserlöeliohmaohende Orupp", ie a · 009816 / -1IΜ ^ i. ·, ■

carboxylic acid group or sulfonic acid group not involved in a metal complex bond, such as of complex bound metal free acidic wool dyes, also complex chromium compounds containing sulfonic acid groups Monoazo dyes in which 1 atom of chromium complex is bound to 1 molecule of azo dyes, containing sulfonic acid groups Phthalocyanine dyes ^ and especially water-soluble Reactive dyes.

The reactive dyes used with preference must have at least one group that is reactive with the nitrogen-containing fiber or one reactive substituent own. Otherwise they can belong to the most diverse classes of dyes, e.g. stilbene dyes, Perinon dyes, peridiearboximide dyes, nitro dyes, triphenylmethane dyes, phthalocyanines But above all the acidic anthraquinones and azo dyes, and although both metal-free and metallizable and metal-containing mono- or polyazo dyes are considered, which Have groupings or a substituent that can react with the nitrogen-containing fibers. The dyes contain at least one, but usually 2 or more acidic, water-solubilizing groups, and particularly good results are generally achieved with dyes which have 3 sulfonic acid groups.

Among the reactive groups mentioned or

Substituents of the reactive dyes are e.g. the ethylene

009815/1066 _BA D

. imide group, epoxy groups, the vinyl group in one Vinylsulfongruppe or in the acrylic acid residue, and especially those labile substituents to be mentioned, which are entrained of the binding electron pair are easy to split off.

As labile substituents, which can be split off with entrainment of the bond pair of electrons, can be mentioned, for example, aliphatically bonded phosphorus or sulfuric acid ester groups, sulfonic acid fluoride groups, aliphatically bonded sulfonyl oxy groups and, above all, halogen atoms, in particular a mobile chlorine atom. These labile substituents are expediently in the y or beta position of an aliphatic radical that is bonded to the dye molecule directly or via an amino, sulfoh or sulfonic acid amide group are in an aliphatic acyl radical (for example in the β-position of a proplonyl radical) or preferably in a heterocyclic ring, in this last-mentioned case both those dyes come into consideration which have a monohalogenated heterooxygenic ring, for example a monochlorinated 1,3 # 5-triazine radical such as the 1,3,5-triazine radical of the formula

- 0 Q-ol

Ϊ 009815/1666

Jv

BATH

wherein X is an alkyl, aryl; Aralkyl, alkyl mercapto or . Aryl mercapto radical, but in particular an optionally substituted amino group or a preferably substituted one Oxy group, as well as dyes with a dichlorotriazine radical or dyes with a dichloropyrimidine radical. There are also reactive dyes with α-bromine or chloroacrylic amino groups with 2,3-dichloroquinoxylinoyl, dihalophthalazine, Dichlorpyridazon, 2-chlorothiazole, ^ propionic acid sulfone residues or radicals of the formulas -CH ^ -NH-OC-alkyl-

Dihalogen, -CHg-NH-OC-alkenyl-halogen or -NH-SOggg -SO-, Η into consideration.

The reactive dyes of the type indicated above can be prepared by methods known per se, for example from dye components which incorporate the named labile substituents or radicals having such labile substituents into the dye molecule after the dye preparation according to methods known per se. By reacting azo or anthraquinone dyes that contain a reactive -OH-, -SH- or especially -NHp group, for example with chloroacetyl chloride, with ß-bromine or ß-chloropropionyl chloride or chloropropionic anhydride, with cyanuric chloride or with primary condensation products of cyanuric chloride, which contain two chlorine atoms and instead of the third chlorine atom of the cyanuric world an organic residue, those reactive dyes which still contain an exchangeable chlorine atom. Such reactive dyes, which a

0098 15 / 1.666 '"J ^

BATH ORIGINAL

have sulfonylated oxy group, can be prepared, for example, that one mole of a single dye containing an oxyalkyl group, e.g., a sulfonic acid N-oxyalkylamide group or a ß-Oxyalkylsulfonic acid with at least one mole of an organic Sulfonic acid halides, e.g. p-toluenesulfonic acid chloride, Benzenesulfonyl chloride or ethanesulfonyl chloride, or with concentrated sulfuric acid or with chlorosulfonic acid like that converts that the oxy group is acylated.

The amounts of the substances to be added to the aqueous dye baths in the present dyeing process can vary within relatively wide limits. The amount of dye depends of course on the desired color strength. It is advisable to measure the amount of the nitrogen-containing compound in amounts of 0.25 to 6%, preferably 0.5 to %, based on the weight of the wool.

However, the amount of nitrogen compound should also be at least 1/4 # (also based on the fiber weight) in light dyeings for which - based on the barrel weight - less than \% dye is used.

Furthermore, it turns out to be two-dimensional, in acidic To stain the medium, so that the p "value of the dyebath is about

2 to 6. This p "value can be increased by adding vinegar

n

acid, if desired also from formic or sulfuric acid, can be set. It is also recommended to use the dye bath sodium sulfate to add. OAD ORIGINAL *

009815/1666

As is generally the case when dyeing nitrogen-containing fibers, especially wool, one works at a higher level Temperature, expediently so that the actual dyeing process begins at about 50 to 80 ° C, to 70 to 80 ° C or heated to the boiling point and continued and ended at this temperature.

To ensure that the nitrogen-containing compound works with certainty from the start, it is recommended that with the dyed material in the bath containing the acid, optionally sodium sulfate, and the auxiliary, i.e. the nitrogen-containing one Compound contains * to enter the dye bath at room temperature or at most moderately elevated temperature to be heated and in the warmth, e.g. at 50 to 80 C, the Add dye in the form of an aqueous solution.

In the following manufacturing instructions vmü. Examples mean the parts, unless otherwise noted, parts by weight and the percentages mean percentages by weight.

0098 15/1668

156S258

Manufacturing regulations

k.) 580 parts (1 mole) of the adduct of one mole of a commercially available pettamine (tallow fatty amine), which
J55 # hexadecylamine, 25 $ octadecylamine and 45 $ octadecenylamine and about 7 moles of ethylene oxide are heated to 60 to 65 ° C.

With stirring, 145 parts are carried in 30 minutes
Chloracetamide, then further in 15 minutes 107 parts of urea and in J> 0 minutes 107 parts of amidosulfonic acids
heated to 95 $ in one hour and stirred for 6 hours at 95 to 98 ^, dissolved in 600 parts of water and obtained about
50 # solution. ( = Preparation A ), which is the compound

n + m j mean = 7

OH ₂ OONH ₂

contains, wherein R is the hydrocarbon residue of tallow lactamine means.

BATH

15/1666

■ Η

■ "ΐ

B.) 58O parts (1 mole) of the adduct from one mole of one commercial fatty amine, which is 35 $ hexadecylamine, Contains octadecylamine and $ 45 octadecenylamine, and about 7 Moles of ethylene oxide are heated to 90 ° C.

120 parts of ethylene chlorohydrin are added in about 15 minutes with stirring and quaternized for 24 hours at 120 ° C. 107 parts of urea and 107 parts of amidosulfonic acid are then added at about βθ and kept at about 95 ° C. for a further 6 hours 600 parts of water are dissolved, and a 50 # Lge solution ( = preparation B ) _{1 is obtained} which is the ammonium salt of the monosulfuric acid ester of the compound

(OH ₂ CH ₂ O) _n H RN> n + mi on average »

GH ₂ GH ₂ OH

contains, wherein R is the hydrocarbon residue of tallow fatty amine means,

BATH 09815/1666

C.) 368 parts (1 mol) of a commercially available alkyl propylenediamine of the formula R-HN- (CH ₂ ) -, - NHp, in which R denotes the hydrocarbon radical corresponding to the soy fatty amine, are reacted with 352 parts (8 mol) of ethylene oxide.

144 parts of the Αααμ ^ εε (1/5 of the amount obtained) are heated to 60 to 658, 50 parts of chloroacetamide are added in 30 minutes with stirring and held for 10 hours at 95 ° to 100% . After cooling to 608, 22.4 parts of urea are added over the course of 15 minutes and 22.4 parts of sulfamic acid are added over the course of 30 minutes. The mixture is then held at 95 to 98% for 6 hours and dissolved in 290 parts of water. This gives tint tajfegt Lotung (PrMpant c ), which is the aqueous salt of the acid monosulfuric acid ester of the compound

01 01 j J

H Ji -— OH ₂ OH ₂ OH ₂ I m + n + p | on average »8

O) _p H

OH ₉ OONH ₅

* * CH ^ OONH,

(OH ₂ OH ₂ O) _n H.

* 2 contains 2 η, where R denotes the remainder of the soy fat «

0098 15/1666 BAD OR.GINAL

D.) The procedure is analogous to procedure A, but the chloroacetamide is replaced by the same amount (145 parts) of epichlorohydrin. An approximately 50 # solution ( = preparation D ) is obtained which contains the ammonium salt of the monosulfuric acid ester of the compound

Cl

(CH ₂ CH ₂ O) _n H.

^RN v n + m ί on average = 7 (CH ₂ CH ₂ O) _m H

CH ₂ -CH-OH ₂ OH

OH
contains, wherein R is the hydrocarbon residue of tallow fatty amine

means.

E.) To 500 parts of the adduct described in Regulation A, Section 1 is added at 60 to 65 ° C. with stirring 93.5 parts (1 mole) of chloroacetamide and lasts for 24 hours at the boiling water bath.

214 parts of urea and 214 parts of sulfamic acid are then introduced at 60 to 65 ° C. and esterification is carried out for 6 hours in a boiling water bath. Hun is dissolved in 440 parts of water, an approximately 50% solution ( preparation E ) containing the compound.

0 0 9 H 1 bi ί 6 8 6 _BÄD

Cl

R N

(CH ₂ CH ₂ O) -SO ₅ NH ₄

n + m: mean = 7

(CH ₂ CH ₂ O) -SO ₅ NH ₄

contains, wherein R- denotes the remainder of the tallow fatty amine.

F.) 480 parts (1 mole) of the adduct of one mole of a commercially available tallow fatty amine, which contains 35 $ hexadecylamine, 25 $ octadecylamine and 45 # octadecenylamine and 4 moles of ethylene oxide are mixed with 145 parts of chloroacetamide for 6 hours at 100 to 105 ° C quaternized. 107 parts of urea and 214 parts of sulfamic acid are then added at 60.degree. C. and esterification is carried out at 100 to 105.degree. C. for 6 hours. It is then dissolved in 660 parts of water and a 40 # Lge solution ( preparation F ) which contains the compound is obtained

(OH ₂ OH ₂ O) _n SO ₃ NH ₄

R *

n + m t on average

CH ₂ OONH ₂

contains, where B means the best of the sebum fatty amines *

009815/1666 ⁸ ^

G-.} Han proceeds in the same way as in Regulation F,

however, uses 795 parts (1 mole) of the adduct of tallow fatty amine and 11 moles of ethylene oxide. After quaternizing and esterification, the mixture is then dissolved in 1220 parts of water, giving an approximately 50 # strength solution ( preparation G ) which contains the compound

Eq

(CH ₀ GH ₀ O) SOJIH

R N

2 2 'n 3 4

n + m: on average - 11

CH ₂ GONH ₂

contains, where R denotes the remainder of the tallow fatty amine.

H.) 665 parts (l mol) of an adduct of one mole of a commercially available fatty amine, which contains about 10 # stearylamine, 55 $ arachidylamine and 35 # behenylamine, and 8 mols of ethylene oxide are at 100 to 105 ° C for 12 hours quaternized with 145 parts of chloroacetamide. At 80 ° C., 107 parts of urea and 214 parts of sulfamic acid are gradually added
and esterifies for 6 hours at 100 to 105 ° C. Then you dissolve in 7βθ parts of water and get about 50 # length
Paste ( preparation H ) containing the compound

009816/1886

Ii * ■ "fi

GH ^ CONH

(GH ₂ CH ₂ OJ

n + m: mean = 8

containsj where R denotes the remainder of the tallow fatty amine.

I.) The procedure is as in instruction A, but the chloroacetamide is replaced by 196 parts of epibromohydrin. After the reaction with epibromohydrin and sulfamic acid, 6 ^ 5 parts of water are then added and an approximately 50 # solution ( preparation I ) is obtained, which contains the ammonium salt of the monosulfuric acid ester of the compound

Br.

β — 3f n + m + on average ■ *

^ (CH ₀ CH ₀ O) H

CH ₂ CH-CH ₂ OH
I.

OH;

contains, where R is the hydrocarbon residue * of the tallow fatty amine means.

K.) The procedure is as in procedure B, but the ethylene chlorohydrin is replaced by 188 parts of ethylene bromohydrii ^ un <J ^Λ ned for 24 hours at 105 to HO ⁰ C.

BATH ORIGINAL

* 00Θ8 15/1666

In this way an approximately 50% solution is obtained (preparation K), which is the ammonium salt of the acid monosulfuric acid ester

the connection *

Br

(CH ₂ CH ₂ O) _n H.

^Err ~ ^N v n + m: mean = 7

(CH ₂ CH ₂ 0) _m H.

CH ₂ CH ₂ OH

contains, where R is the hydrocarbon residue of the tallow fatty amine.

L.) 580 parts of the adduct described in Regulation A, Section 1 are mixed with 145 parts of chloroacetamide for 12 hours 100 to 105 ° C quaternized and then dissolved in 500 parts of anhydrous pyridine.

The solution obtained is slowly added with stirring to a solution prepared at 5 ⁰ C solution of 256 parts of chlorosulphonic acid in l400 parts of anhydrous pyridine.

It is then held for 3 hours at 40 to 45 °, then neutralized at 20 to 30 C with 3Gj6iger caustic soda, sucks off and sells the volatile from the piltrate by distillation in vacuo Shares. The residue is dissolved in 80 parts of water and it

a product is obtained (Fra ^ arat. $ » which about

Link . . ·

00 9 8 15/1666

Cl

(CH ₂ CH ₂ O) _n SO ₅ ITa

^R * v n + mj on average «7

CH ₂ CONH ₂

contains, where R is the remainder of the tallow fatty amine.

M.) 580 feile (l mol) of the Ädduktes described in Procedure A, paragraph 1, quaternized with 122 parts Chlora'oetamid 2k hours at 95 to 100 ⁰ C. At 8O ⁰ C to wear it, 108 parts of maleic anhydride in 30 minutes and then holding for 30 minutes at ICO ⁰ C and 30 minutes at 120 ⁰ C. Then are added at j? ris 109 ⁰ C ? 80 parts of water and 200 parts of sodium self. '.,; Vu: -Bi ::> eld further 1 hour at 95 to 100 ⁰ C * Man,

the connection

dl

80 ».la

rtm ΐ i & .Mittel, »

BATH ORIGINAL

example

r <ss t * (S9- ti »it?

■ In a ■ Strjangfärbe-Äppsra-f be-; 100; kg

yarn in 2Q (DXifces ⁹ - Vlasses ⁵ -10 Minuten-- at 50 ⁰ C ^-v: orjg @ netafe it sets I _1, 5 _"FL 10 kg SisBSsig kg crystallized sulfate, a kg of the preparation A.." andl kg. des-Rotea the formulaic "" ■ ^-:. "^'-...

HOrCBLHJH,

to "Man steigerfe" oils T colors at ifeohteffipemfcu -kühltj, - Kalt''pulte.uhö massive ie

tn -Ί5- Minufctn stars on this

step

@i

öer

F ^ Spa ^ afe fi, feisiö

pack «" iceina-

des fii? tee5Htiis on

Saliiuffi@ii.mid Iteiia

a © ig © a aiefefe ^

is j

wasiaSPlÖgäääßU Is fe © iaiBfe öesäalb

_BATH

Similar results are obtained with the dyes of the following formulas,

SO ₃ H NH ₂

(Red) ,,

^ä I H0- <I>

Oi 0

SO _x H ν

HO ₃ S

O- «OH

¹ C / ~ HN-AAA-SO ₃ H ^ j ( _Orainee )

Cl

Oj //

-0 SO

λλ »Jl

SO-H j

^ _H " ^ß AD ORIGINAL

b D 6

56825-8

ιίgame 2

■ Kreuzspüleri auö '''v © r »ehloriert®ffi Mollgam old Ifiöö water b <si 5bS- ^i0; -MlB" fen aingepet ^ t / Seim © rfolgfe- of ·· addition of 5 feg acetic 80 IQ kgic Sodium sulfate ». '1 * 5 kg des.'.. ■ ■

'-Preparations.- B ^: -νααά-% feg-; of the ioten dye & the

b & iiidesi i; ia ^ Mfeoi'j S ^>! r ^ si- ¹ T ¹ Jj "/,:,. ' si- mO tXjcI "Ά12ι

'κ

BATH

i # i8! S / " ^: s§s

in this example, instead of preparation B, the same

** "Amount of preparation A, C, D or E or that in example 1 specified dyes are used.

specified dyes are used.

Example j

4 pieces of woolen fabric weighing 100 kg in total are wetted in 4000 liters of water at 50 ° C. on a reel skid. Then 5 kg of sulfuric acid, 10 kg of crystallized sodium sulfate, 2 kg of preparation C and 0.46 kg of 1: 1 chromium complex of the dye of the formula are added

HO

(blue)

0.40 kg l: l chromium complex of the dye of the formula

HO JH
HO <

jS <3H = H <t

"""* (red) and

0.21 kg lil-chromium complex of the dye of the formula

HO-S PH

O ₂ HO-flH- <I>

0 009815/1666

It is heated to boiling temperature in 45 minutes and cooks I hour. It is then fed in with cold Water slowly cooled, rinsed thoroughly, centrifuged and dried. Pieces of gray nuance also result good surface and fiber level. During dyeing, the pieces do not tend to swim, but are instead always in the dye liquor (with the exception of the route via the dye reel, of course). Furthermore, there are no precipitations

Example 4

100 kg are loose in a circulation apparatus Wool (flake) wetted in 2000 liters of water at 50%. then 2 kg of glacial acetic acid, 10 kg of crystallized sodium sulfate, 2 kg of preparation D and 1 kg are added of the blue dye of the formula

It is heated to high temperature in 60 minutes and boils for 60 minutes, then rinsed and dried. The result is a level turquoise-blue color of good Eoht «

0098 15/166 6 -

■ · ■ .. ■ BATHROOM

units. No disturbing foaming occurs during dyeing. Because of the special behavior of preparation D do not form any channels in the material block, the levelness is excellent.

Example 5

100 kg of cheeses made of pure wool are packed in a package dyeing machine. In the preparation container The following liquor is prepared for this apparatus:

1200 liters of water of 50 ^ are presented. In addition

to give

5 kg of sodium sulfate,
2 kg glacial acetic acid,
1 kg of the dye given in Example ΐβ

Formula and finally 1 kg of preparation D.

This dye liquor is pumped into the package dyeing machine, heated to boiling temperature in 40 minutes and boiled for 1 hour. Then it is rinsed thoroughly and dried. A level, turquoise-blue dyeing with good fastness properties is obtained. During dyeing, the cheeses are not deformed and _e3 no channels are formed in the material.

BATH ORIGINAL

009815/1666

. Example 6

In a Kreuzspulapparat 100 kg wool yarn are wetted in 'Porm of cross-wound bobbins in 2000 1 of water at 50 ⁰ C for 10 minutes. Then 6 kg are added. Sulfuric acid, 10 kg of crystallized sodium sulfate, 1 kg of preparation A and 1 kg of the red dye of the formula

HO, S

Gr!. {.! - complex

The temperature is increased to 80 ° C. in 30 minutes and stains at this temperature for 1 hour. Subsequently i | rlrd rinsed and buffered with sodium acetate. The result is a level, genuine red dyeing of the woolen thread. The packages are not deformed »·

Instead of preparation A, the preparations For urid I »are also used» the dyes of the following Formulas can be used with equal success;

'■ - ■' ■■. ■■■. ^:::: HO SO _x Ia. -

01

9815/1866

HO

JiWwÖ

OH

C-

Ψ-Ο

Cr lil complex

(orsunge) 0H

OH

HO _n

(orange)

σ —- κ—- <d>

Cr lJl complex

Oh

HO

ν-ar

UJ

(blue)

HO

OH

= K 0 H

(pink)

CH,

OH

Or lil complex

Oz * 111 ~

Or 1 ', 1 complex

BATH ORIGINAL

. ■ '■. - example- 7 ^; '

- ■ ■ In a "cross-spool dyeing machine, 100 kg

■ ■ ο

. "Porro- from: Kreuzspule ^ in 1500 1 Masser at -50 ° C - netting up during the whole time» This is followed by dssr Itissres ¥ oa 5 ^ 5 ^ g. Sulfuric acid 96 $ ig, 10 kg-toistallisiertss Siefcriyissua 1 kg of the preparation S- imä 2 kg of the par "substances from example - & _e -; ■ -. ■. ■ '· -. .. '- -

^ ti © Ffe -'die

lcoeat- 1 -Stuscte ^ aESßIiI: legs @ aö will gsiiaetlieti g@spili3.fe.

\ § kcSsKQE smell. άχ® Fi ^ ga ^ ate..H lsi, 8 '■ ..- """-'

Bts * angf ^ rb © aPpSi ⁵ St- be IöQ-! Cg Moilgafn Ie k. 2000 "! ¥ ater," uates? Eusatg ^ 8ö to § kg of acetic acid ^e] i nn <8 preparation Ä wllii ^ ni 1 ©. KÄsutsa-¥ oil "g © aet, zt" Daria done Zusats from 3 kg to s dye of Föratl ■

Oll Ω ft 1 P i ί / R is f5 ö i ei J a / I & © b

Kai increases the temperature to 70 ⁰ C in 30 minutes and colors! 50 minutes at this temperature. It is then rinsed and dried. The result is a level, true red discoloration of the wool yarn. The above dye can also be replaced by dyes from? Oraal

^C1

HO-S- ~ d> ~ - # = ~ S-CH S0 ~ H

HO IHCOOH ₃
SO ₃ H

(Red)

ϋ 3ίΗ ,.

v " (blue)

BATH ORIGINAL

009815/1666

HO B8H3Ö.

In βίββε * S in Sooft i 10 leg b IO Minuter «

ϊιβΐ 50 ⁰ p

H ₂ C = COCNH go ^ _(red)

Br

It is heated to the boil in 40 minutes and cooked for an hour whereupon 3 kg of ammonia 25 # ig is added, for 20 minutes in Treats the cooling bath, rinses and acidifies in the last rinsing bath with 1kg formic acid 85%

The result is a real, lively and level red dyeing of the wool. Instead of the above dye you can the following dyes can also be used:

OH HO ₃ SOCH ₂ CH ₂ SO ₂ ON == N-jjVj NHCOOH ₃

(orange) cvif HO ₃ S "9
SO HO ₃ SOCH ₂ CH ₂ SO ₂
(Red) 3 ^H.

* 4.

BATH ORIGiMAL 009815/1666

* HO HO-SOCH ₂ CH ₂ SO ₂ / Ν-N == N / SA

OCH- HO ₅ S SO ₅ H

(Red)

(Red)

SO ₅ H

HO ₃ S

KHOOC = CH ₂

H ₂ C = COCNH " ^W 3"

Br

(orange)

HO ^ S I HJ If

YYV — OHgffHGQOH— (Η,

SO "H Br Br

(Red)

OHHH ₀ SO _x H

s 1. 2 ■ s 5

SO "H
IHCOOH-CH ₂ ^{y 3} -.MOOGH-OH ₂

I I

^BrBr (blue) ^ ^Br

00aβ 1 s / 16

OH
Λ-N == N NCOC = CH ₀

Cr 1: 2 complex

(Gray)

Example 10

In a cheese dyeing 100 kg Cross coils 2 kg of acetic acid 8θ be prewetted # and 10 kg of crystallized sodium sulfate for 10 minutes at 50 ⁰ C in 2000 1 of water with the addition of 2 kg K preparation. Then 2 kg of the dye of the formula are used

SO-H HO HWCO  <_> "

A N = If ΛΛ HN C C — oil

HO-S-A / HO-SAAZ-SO-H I I

⁵ * ^ Cl-O N

(red) Cl

It is heated to the boil in 30 minutes and cooked an hour is then rinsed and dried. The result is a level and real dyeing of the wool yarn. During the The cheeses are not deformed during dyeing.

^ 'ORIGINAL 009815/1666

Claims (1)

Claims 1. Use of amphoteric polyglycol compounds containing a) a nitrogen-bonded aliphatic hydrocarbon radical with 12 to 24 carbon atoms and b) (CH ₂ -CHg-Q-) _k ~ groups bonded to nitrogen, where k is a whole positive number and a total of 4 to 12 -CH ₂ -CHp-O groups are present in the molecule, which on the one hand quaternizes with organic halogen compounds and on the other hand esterified with at least dibasic oxygen acids to form acidic ester groups, as a leveling agent when dyeing nitrogen-containing, fibers that can be dyed with acidic dyes. 2. Use of amphoteric polyglycol compounds, which differ from organic halogen-containing quaternizing agents and from acidic esters of the formula R- —Ec -N BATH 0 9 8 15/166 6 1563258 derive, where R is a preferably unbranched, aliphatic hydrocarbon radical with 12 to 24 carbon atoms, X is the radical formed by separation of an HO group from a polybasic organic acid, m is the number 0 or 1, η is the number 2 or ~ $, s is a whole Number with a value of at most 2 + m and p, q and r are whole numbers, the sum p + q + r being 4 to 12, for the purpose indicated in claim 1. J>. Use of amphoteric polyglycol compounds according to one of Claims 1 and 2, the quaternary nitrogen atoms of which are bound to chloroacetamide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin or epibromohydrin, for the purpose indicated in claim 1. 4. Use of amphoteric polyglycol compounds according to one of claims 1 to ~ 5, which contain acidic sulfur, acid ester groups, for the purpose specified in claim 1. 5. Use of amphoteric polyglycol compounds according to one of claims 1 to 4, as a leveling agent when dyeing whole fabrics with acidic dyes. 6. Use of amphoteric polyglycol compounds according to one of claims 1 to 4, as leveling agents in dyeing of wool with acidic reactive dyes or acidic 1: 1 metal complex dyes.