DE2502154A1 - METHOD OF DYING HYDROPHOBIC FIBERS - Google Patents

Description

The invention relates to a method for dyeing hydrophobic Fibers using disperse dyes.

It is known to use hydrophobic fibers in the presence of a dyeing aid to color. These are usually water-insoluble compounds in the form of an emulsion be applied.

British Patent 1,021,806 describes a preparation for dyeing hydrophobic materials, e.g. polyester fibers, which contains an acetate dye, an aryl glycol ether the general formula. '

509830/0970

.Ar (OCH ₂ CHH) _n OH

wherein R is hydrogen or methyl, Ar is an aromatic hydrocarbon st off the rest of the benzene series', optionally by halogen or U-lower alkyl, and η is the number 1 or 2, and contains a di- or trichlorobenzene. However, these dye preparations are at a temperature of

ti '

8 5 ° C to the boiling point of the bath at atmospheric pressure, in particular at about 90 ° C, used.

In the German patent 1 001 966 is a method for Dyeing or printing of polyester fibers with disperse dyes in the presence of Pheiiolo :: yalkyl ethers or lower alkylated or monochlorine derivatives thereof. This procedure is performed in the presence of a surfactant Boiling temperatures carried out.

In British Patent 1,328,107 there is one method for dyeing polyester fibers using an aqueous Dye liquid (dye liquor) described containing a disperse dye and a compound of the formula

EO - (- CH ₂ CHXO H

wherein R is a phenyl radical or a chlorine-substituted phenyl radical, η is an integer from 1 to 3 and X is hydrogen or methyl, where X is methyl if η = 1, and at least one of the radicals X is methyl, v / enn η = 2 or 3 »

509830/0970

"^" 5502154

or a compound of the formula.

EO -4- CH ₂ CH ₂ O) _ H

where R is a chlorine-substituted phenyl group and η is a whole Number from 1 to 3, contains, in the absence of a di- or trichlorobenzene or an added emulsifier.

In the Belgian patent 792 403 a method is described, in which a polyester is dyed using an aqueous dye liquid containing a disperse dyestuff ^ · contains substance, an emulsifying agent and a compound or a mixture of compounds of the formula

\ O (R'O-fcH

^C1 n

where η is an integer from 2 to 5 »R ¹ denotes an ethyl or isopropylene radical and m denotes an average value of not more than 3, in the absence of a di- or irichlorobenzene. -

The invention is a method for exhaust dyeing of hydrophobic fibers at 110 to 135 ⁰ C with a disperse dye in the presence of an adduct of an average of 1 to 4 moles of ethylene oxide, propylene oxide or styrene oxide or a combination thereof

0/0970

and 1 mole of a phenolic compound of the formula

^R 2

where "mean:

η is a number from 1 to 4,

E ^ j hydrogen, chlorine, a straight (unbranched) or branched one An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group with 2 to 8 carbon atoms,

Rp is a straight (unbranched) or branched alkyl group with Λ to 8 carbon atoms, an alkenyl group with 2 to carbon atoms, a cycloalkyl group with 5 "to 8 carbon atoms, which may be substituted by one or more alkyl groups with 1 to 4 carbon atoms, preferably a methyl group can, a cycloalkenyl group with 5 ^ is 8 carbon atoms, an aralkyl group with 7 ^ iS 9 carbon atoms, which can optionally be substituted by an • alkyl group with 1 to 4 · carbon atoms, an aralkenyl group with 2 to 3 carbon atoms in the alkenyl radical, a hydroxymethyl or COOH ₅ , group, in which R, denotes a phenyl group which is optionally substituted by alkyl having 1 to 4 carbon atoms,

609830/0970

Aryloxyalkyl, in which the alkyl part contains 2 or 3 carbon atoms and the aryl part optionally by one. or more chlorine atoms or one or more straight (unbranched) or branched alkyl groups having 1 to 4 carbon atoms may be substituted, or a Aralky! group having 7 to 9 carbon atoms, or a biphenyl hydroxy ä thy1 group, with the proviso that

a) the total number of carbon atoms in (E ^) _n _ ^ does not exceed 8,

b) if η = 1 and Ep = alkyl, the alkyl group at least Contains 2 carbon atoms, and

c) if the adduct is derived from styrene oxide, Rö Mean hydrogen or chlorine.

The quantitative ratio of ethylene oxide, propylene oxide, styrene oxide or a combination thereof is preferably an average of 1 ha to 1 mole of the phenolic compound of formula (1). One preferred adduct group is that of one unit Ethylene oxide is derived.

When R ^ j and / or E _{2 are} alkyl groups they preferably contain 1 to 4 carbon atoms, and when R ^ is an alkoxy group it preferably contains 1 to 4 carbon atoms and "· ._ when R ^, and / or Ep Are alkenyl groups, they preferably contain 3 or 4 carbon atoms _o

Examples of R ^ are chlorine, methyl, ethyl, isopropyl, t-butyl,

509830/0970

sec-butyl, t-octyl, allyl, 2-butenyl and methoxy.

Examples of R ₂ are methyl, ethyl, isopropyl, t-butyl, sec-butyl, heptyl, t-octyl, allyl, 2-butenyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclopentenyl, cyclooctenyl, benzyl, α-methylbenzyl, a- jOc-Dimethylbenzyl or COOR, groups, in which R ^ is phenyl, isopropylphenyl, 2-phenoxyethyl, 1-phenoxy-2-propyl, benzyl and 2-phenyl-2-hydroxyethyl.

Particularly valuable adducts according to the invention as dyeing auxiliaries are the adducts or mixtures thereof enumerated in Sections A and B below are.

A) Adducts of the formula

CH-CH-O- ^ H (2) X ₁ X ₂

v / orin R ^ and η have the meanings given for the formula (1) have, R ^, a straight (unbranched) or branched alkyl group with at most 8 carbon atoms, an alkenyl group with 2 to 8 carbon atoms, a cycloalkyl group with 5 up to 8 carbon atoms containing one or two alkyl groups with 1 to 4 carbon atoms, preferably a methyl group, may contain a cycloalkenyl group with 5 to 8 carbon

509830/09 70

atoms, a phenylalkyl group containing 1 to 3 carbon atoms. in the alkyl radical, which is optionally substituted by alkyl with 1 to 4 Carbon atoms in the "benzene nucleus can be substituted, one. Phenylalkenyl group with 2 to 3 carbon atoms in the alkenyl radical or a hydroxymethyl group, one of the radicals X ^ and Xp is hydrogen, methyl or phenyl and the other is hydrogen and m is a number from 1 to 4, preferably the number 1, mean, with the proviso that

a) the total number of carbon atoms in (IL ₁ ) -. *, if

ι η— ι.

Present, at most 8,

b) if η = 1 and E ^ = alkyl, the alkyl group contains at least 2 carbon atoms, and

c) if one of the radicals X ^, and, Xp is phenyl, E ^, can also Be hydrogen or chlorine.

A preferred class of compounds among the compounds of the formula (2) are those in which E ^ and E ^ are straight (unbranched) or branched alkyl having a total of 3 to 7 carbon atoms. Particularly preferred compounds within this class are those in which η = 1, ie in which only R _{1 is} present «, '

A second preferred group of compounds of formula (2) are those in which E ^ is hydrogen, methyl or chlorine, η the Number 2 and E ^ cyclopentyl, cyclohexyl, benzyl, α-methylbenzyl or α -, - cc ^ mean dimethylbenzyl.

509830/0970

A third preferred group of compounds of the formula (2) are those in which R ^ and R ^ independently of one another are hydrogen or chlorine, one of the radicals X 1 and X ^ is phenyl and the other is hydrogen, m is the number 1 or 2, preferably the number 1, and η the number 2 to 4-, preferably the number 2 or 3, mean.

B) Salicylate adducts of the formula

COOR

CH - CH J I. ^X l X,

wherein R ^, R ^ and η have the meanings given for the formula (1) and X ^, Xp and m have the meanings given for the formula (2) own. In the formula (3) given above, R is preferably benzyl and particularly preferably phenyl, R> i Hydrogen, one of the radicals X ^ and X ^ means hydrogen or methyl and the other .hydrogen and m stands for the number 1.

Examples of adducts as defined above those in the process according to the invention as dyeing auxiliaries can be used are the following:

609830/0970

2- (2-chloro-6-methylphenoxy) ethanol. ·

1- (2-chloro-6-methylphenoxy) propan-2-ol 1- (4-chloro-3-methylphenoxy) propan-2-ol or ethanol.

2- (2,4-Mchlor-6-methylphenoxy) ethanol 2- (4-chloro-3,5-dimethylphenoxy) ethanol 1- (2,4-dichloro-6-iaethylphenoxy) propan-2-ol 2- (2,4-dichloro-3,5-d.ine thy lphenoxy) ethanol

2- (2-Isopropylphenoxy) ethanol · ·

2- (o-ethyl-phenoxy) ethanol or 2- (p-ethyl-phenoxy) -ethanol 2- (4-isopropylphenoxy) ethanol or 2- (heptyl-phenoxy) ethanol 2- (p-t-butylphenoxy) ethanol or 2- (p-octyl-phenoxy) ethanol 2- (2-chloro-4 ~ t-butylphenoxy) ethanol

2- (2,3 »5-triniethylphenoxy) ethanol · '

2- (2,6-Di-isopropylpheiioxy) ethanol 2- (2-t-butyl-6-methylphenoxy) ethanol 2- (2-allylphenoxj ⁷ ) ethanol 2- (2-methoxy- ^z } ~ all3 ^r lphenoxy) ethanol

2- (2-Isopropyl-4- chlorophenoxy) ethanol

2- (2,6-di-sec-butylphenoxy) ethanol

1- (o-Benzylphenoxy) ethanol or i- (p-Benzylphenoxy) propan-2-ol

1- (2-Benzyl-4-chloro-phenoxy) propan-2-ol

2- (o-a-methylbenzylphenoxy) ethanol

i- (p-α-methylbenzylphenoxy) propan-2-ol 1- (p-a, a-Dimethylbenzylphenoxy) propan-2-ol 2- (p-Styryl-phenoxy) ethanol 2- (p-a, a-Dimethylbenzylphenoxy) ethanol -i- (2-Isopropyl-4-α, α-dimethylbenzylphenoxy) propan-2-ol

509830/0970

1- (2-Benzyl-4-chlorophenoxy) propan-2-ol 2- (2- * Isopropyl-4 ~ oc, ad.ime thy Ib enzylphenoxy) ethano 2- (p-Cyclopentylphenoxy) ethanol 2- (p -Cyclohexy! Phenoxy) ethanol 2- (p-cyclooctylphenoxy) ethanol 1- (p-cyclohexylphenoxy) propan-2-ol 1- (p-2-cyclopentenylphenoxy) propan-2-ol 1- (2-isopropyl-4-cyclohexylphenoxy ) propan-2-ol 1- (p-Cyclopen.ten-2-yl-phenoxy) propan-2-ol 1- (o-isopropyl-p-cyclopenten-2-ylphenoxy) propan-2-ol 2- (p -1-methylcyclohexylphenoxy) ethanol 2- (o-hydroxymethylphenoxy) -1-phenylethano1 2-phenoxy-1-phenylethanol or 2 ~ phenoxy-2-phenyl-a1; ethanol diethylene glycol mono-pt-butyl-phenyl ether diethylene glycol mono-p -cyclohexyl-phenyl ether, a-Konde nsationsprodukt of 1 mole of 4-chloro-in-cresol and ^ - mol propylene oxide, a Kondensationsprodtikt of 1 mole of 4-chloro-3,5 ~ ^x ylenol lind 3 ethylene oxide Koi

Phenyl o ~ (2 ~ hydroxyethoxy) benzoate phenyl o- (2-hydroxypropoxy) benzoate benzyl 2 ~ (2-hydroxyethoxy) benzoate benzyl 2- (2-hydroxyethoxy) -6-methylbenzoate 2-isopropylphenyl-2- (2-hydroxy-propoxy) benzoate 2-phenoxyethyl-2- (2-hydroxy-1-propoxy) benzoate 2-hydroxy-2-phenylethyl-2- (2-hydroxy-1-propo: ^ r) benzoate 1- ( 2 ₁ 4-dichlorophenox2r) prop-2-yl-2- (2-hydroxyprop-1-o: iy) benzoate

509830/0970

. - 11 -

2- (o-Isopropylphenoxy) ethyl 2- (2-hydro-prop-1-oxy) benzoate 1-phenyl-2-hydroxyethyl benzoate or 2-phenyl 1-2-hydroxyethyl benzoate.

Adducts of formula (1) that do not contain chlorine are off preferred for ecological reasons.

In the. hydrophobic fiber can be, for example, a cellulose triacetate fiber, which is the present invention however, particularly applicable to linear polyester fibers, especially polyethylene glycol terephthalate fibers.

In the case of the disperse dye used according to the invention, can it is, for example, an azo, anthraquinone, nitro, Methine, styryl, azostyryl, mtroacridone, coumarin, uaphthoperinone, Act quinaphthalone or naphthoquinone imine dye.

The amount of dye used in the dye liquid depends on the circumstances and it can be up to 10% by weight, based on the weight of the fiber to be dyed.

The adducts defined above can be used in various ways. For example, they can be used alone or, you can with an emulsifier, 2.B- * a sulfated alleylphenol-ethylene oxide adduct, and optionally an organic solvent, such as isopropanol, 'mixed' are forming a homogeneous, self-emulsifiable Product that can be added to the hardening bath.

509830/0970

When the adducts defined above have a low solubility in water and are used in dyeing devices in which surfactants of the above type are used tend to be excessive Foaming ,, Under these circumstances, the adducts be mixed with low sudsing surfactants which are synthetic or natural in origin, e.g. sulfited fish oils »

The inventive method is discontinuous (batchwise) carried out and the adduct defined above can be added directly to a dye bath. The temperature at which the Dyeing is carried out, is usually 110 to 135 ° C, preferred ■ in a so-called high-temperature dyeing process wise 115 "to 135 ° C <> The duration of dyeing depends on the circumstances, but generally a period of up to 2 hours is sufficient. The amount of the adduct defined above can be within the range from 0.5 "to 2, preferably from 0.1 to 1% by volume, based on the total volume of the aqueous dye liquid,

lie.

The dyeing can, if desired, be completed by transferring the fiber to a separate bath in which it is subjected to a reduction clarification process to remove the surface dye. The fiber can then be rinsed (washed) and dried. The dyeing process is suitable for the use of loose material, yarn, woven / -

609830/0970

knitted fabrics and carpets. Except on fibers that are completely made from a single hydrophobic fiber such as polyester or cellulose triacetate can do that dyeing process according to the invention also on mixtures of textile fibers, such as »polyester fibers together with other fibers, such as wool, cotton, acrylic, cellulose or polyamide fibers containing mixtures.

The dyeing process according to the invention is particularly valuable when used in modern high-temperature dyeing devices such as jet, reel or pack dyeing devices and it was found that the thereby obtained colored Material better leveling properties, higher color yield than when using, for example, monochlorophenoxyethanols and cresoxyethanols *

The invention is explained in more detail by the following examples, but without being limited to it. Unless otherwise stated, the parts specified therein relate to, on weight. Parts by weight have the same relationship to parts by volume as kg to liters.

Example 1 . '

4 parts of one. Polyethylene terephthalate (Crimplene) fabric were in 160 parts by volume of an aqueous dye liquid (Dye liquor) immersed that contained

509830/0970

a) 0.12 parts of a dye that is a mixture of

N = N

—N = N

N = N -

, _N = N

SO ₂ NHCH ₂ CH OH

acted in a ratio of 1: 1, and

b) 0.32 part of 2- (2-chloro ~ 6-methyl-phenoxy) ethanol.

The pH was adjusted to 5 to 6 with acetic acid and the dyeing was carried out ^{at a temperature of 120 ° C. for 1 hour.} The tissue was then transferred to a separate bath which contained 160 parts of an aqueous liquid, which in turn contained 0.8 part of a sodium hydroxide solution at 70 ° Tv /, 0.32 part of sodium dithionide and 0.32 part of an ethylene oxide condensate of stearyl diethyl trxamine, and Treated therein at 70 ° C. for 30 minutes. The fabric was then rinsed in warm water and dried. It was an equal

609830/0970

r 15 -

moderate red color with a good color yield .. '·

• Example 2

4 parts of a polyethylene terephthalate "," (Crimplene) fabric were in 160 parts by volume of an aqueous dye liquid (Dye liquor) immersed, which contained: a) 0.12 part of a dye which is a Mix of

OCH

Ν— (

SHCOCH

CH ₂ CH ₂ OCOCH ₃

OCH

CH ₂ CH ₂ OCOCH ₃

KHCOCH

acted in a ratio of 3: 1, and "b) 0.32 parts of 1- (2 ~ chloro-6-methylphenoxy) propan - 2-ol.

The pH-T7ert was adjusted to 5 - & is β with acetic acid and dyeing was carried out at an iron temperature of 120 ° C for 1 hour carried out. The gev / ebe was then transferred to a separate bath, which contained 160 parts of an aqueous liquid which

509830/0970

in turn 0.8 part of an I sodium hydroxide solution at 70 ° Tv /, 0.32 part of sodium dithionite and 0.32 part of an ethylene oxide condensate of stearyl diethylenetriamine, and 30 minutes treated for a long time "at 70 ° C". The tissue was then placed in Rinsed with warm water and dried. A uniform navy blue coloration with a good color yield was obtained.

Example 3

Using a similar procedure to Example 1, "but this time using 0.32 parts of 1- (2, ^z l-dichloro-6-methylphenoxy) propan-2-ol in place of component (b), a uniform coloring obtained with a good color yield.

Example 4

2fold a similar procedure as in Example 1, this time but 0.32 part of 1- (4- chloro-3- 3Qethylphenoxy) propan-2-ol instead of component (b) were used, uniform coloring was obtained with a good color yield.

example 3

Following a similar procedure as in example i, this time with jjedoch 0.50 parts of the self-emulsifying agent specified below Oil were used instead of component (b), a uniform coloration was obtained with a good color yield, Bas self-emulsifying used as dyeing aid in this example Oil was made as follows:

5098 30/0970

One with a stirrer, one thermometer, one with one

A reflux condenser connected to a cold trap and a flask fitted in a gas inlet tube gave 156.6 parts of 4-chloro-3,5-ocylenol and introduced 1 part of finely powdered sodium hydroxide. The device was initially purged with nitrogen and became very slow during the itoxylation Maintain nitrogen flow. If you maintain a Temperature of 140 to 160 ° C were 130.3 parts of ethylene oxide gradually to the stirred mixture over a period of Added for 105 minutes and the reaction mass was then allowed to cool calmly. It became diisopropyl ether in 1250 parts by volume dissolved and placed in a separating funnel until neutral Washed water (5 times 100 parts by volume). The solution was then dried and filtered. The solvent was then distilled off.

A self-emulsifying oil was made by mixing of 69 parts of the adduct given above, 13 parts of isppropanol and 13.5 parts of the sodium sulfate ester of a commercially available one Nonylpheno1-ethylene oxide adduct in 4.5 parts of aqueous ethanol.

Example 6

Following a similar procedure to Example 1, except that this- ' times, however, instead of component (b) 0.64 parts of a self- emulsifying oil is used, which is obtained by mixing 40 parts of 2- (2,4-dichloro-6-methylphenoxy) ether inol, 28 parts Isopropanol and 9 parts of the sodium sulfate ester of the commercially available

«09830/0970

Union nonylphenol-ethylene oxide adduct was prepared in three parts of aqueous ethanol, became a uniform color obtained with a good color yield.

Example 7 '

Following a similar procedure to Example 1, this time with However, instead of component (b) 0.64 parts of a self-emulsifying one Oil were used by mixing 40 parts of 2- (4-chloro-3,5-dimethylphenoxy) ethanol, 28 parts of iso- ■ propanol and 9 parts of the commercially available sodium sulfate ester Nonylphenol-ethylene oxide adduct in 3 parts of aqueous ethanol was produced, uniform coloring was obtained with a good leveling color yield.

Example 8 '

Following a similar procedure to Example 1, this time with but 0.64 parts of the self-emulsifying agent specified below The oil used was uniform in color without an excessively good color yield. The self-emulsifying oil used in this example was as follows manufactured: .

One with a stirrer, one thermometer, one with one

Cold trap connected reflux condenser and a gas inlet pipe equipped flask, 191 parts of 2,4-dichloro-3 »5-xylenol and introduced 1 part of finely powdered sodium hydroxide. The device was initially run with nitrogen.

509830/0970

- ■ / 19- ■ · "■■■

rinsing and during the ethoxylation a very slow · Maintain nitrogen flow.

While maintaining a temperature of 140 ° C., 44.4 parts of ethylene oxide were gradually added to the stirred mixture over a period of 115 minutes before it was allowed to cool. The solid product was recrystallized twice from di-n-butyl ether to give 119 , 2 parts of 2- (2,4-Diehlor-3,5-dimethylphenoxy) ethanol, F. 99 to 100 ⁰ C.

analysis

"Calculated: G 51.00 H 5.15 Cl 30.16 found: 51.01 5.12 30.36%.

A self-emulsifying oil was made by mixing 20 parts of 2- (2,4-dichloro-3,5-dimethylphenoxy) ethanol, 54 parts Isopropanol and 4.5 parts of a commercially available sodium sulfate ester Nonylphenol-ethylene oxide adduct in 1.5 parts of aqueous ethanol.

Example 9

Following a similar procedure as in Example 1, except that this times, however, 0.5 part of a self-emulsifying oil was used were obtained by mixing 69 parts of 2- {2-Chlqr-4-t-butylphenoxy) ethanol, 13 parts of isopropanol and 13.5 parts of one Liatriuasulfatester of a, commercially available monylphenol-ethylene oxide adduct was made in 4.5 parts of aqueous ethanol, uniform coloration with excellent Color yield obtained.

809830/0970 - - ■ · "

Example 10

In a similar procedure to Example 1, except that 0.25 part of the self-emulsifying oil indicated below was used instead of component (b), a uniform coloration was obtained with an excellent color yield. The emulsifiable oil used as a dyeing aid in this example was prepared as follows:
One with a stirrer, one thermometer, one with one

Cold trap connected reflux condenser, a gas inlet pipe and a dropping funnel, 3 parts of finely powdered sodium hydroxide and 578 parts of a Phenolic mixture introduced with the following ingredients:

Phenol 30.8%

o-isopropylphenol 34.6 %

m / p-isopropylphenol 12.3 %

2,6-diisopropylphenol 6.4 %

2,4-diisopropylphenol * 10.7%

. 2,5 / 3,5-diisopropylphenol 2.5 %

2,4-, 6-triisopropylphenol 2.5 %

2,4,5-triisopropylphenol 0.2 %

The device was initially purged with nitrogen and a very slow nitrogen flow was established during the propoxylation maintain

609830/0970

. - 21 -

While maintaining a temperature of 140 ⁰ O, 188.8 parts of itopyylene oxide were added over a period of 220 minutes and the reaction mixture was allowed to cool. The reaction mass was then washed 10 times with 20 parts by volume of a saturated saline solution and dried at a pressure of 12 mm, whereby the adduct was obtained in a yield of 542.9 parts.

A self-emulsifying oil was made by mixing of 85 parts of the above adduct and 11.2 parts of a sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 3j8 parts of aqueous ethanol.

Example 11

Following a similar procedure to Example 1, this time with however, instead of component (b) 0.25 part of a self-emulsifying oil was used which was obtained by mixing 85 Ropes 2- (o-iso-propylphenoxy) ethanol and 11.2 parts of a sodium sulfate ester of a commercially available NOnylphenol-ethylene oxide adduct in 3 »8 parts of aqueous. Ethanol was made uniform in color with excellent Color yield obtained.

Example / 12

Following a similar procedure as in Example I _1, but this time 0.25 part of the self-emulsifying oil specified below was used instead of component (b),

509830/0970

became a uniform coloration with an excellent one Color yield obtained. The self-emulsifying oil used in this example was prepared as follows: One with a stirrer, one thermometer, one with one

68 parts of 4-isopropylphenol and 0.5 parts of finely powdered sodium hydroxide were introduced. The device was initially flushed with nitrogen and a very slow nitrogen flow was maintained during the ethoxylation.

While maintaining a temperature of 140 C were 25.2 parts of ethylene oxide to the stirred mixture via a Added period of 37 minutes. The reaction mixture was washed 10 times with 10 parts by volume of water at a pressure of Dried 12 mm and 88.2 parts of 2- (4-isopropylphenoxy) ethanol were obtained.

A self-emulsifying oil was made by mixing 85 parts of 2- (4-isopropylphenoxy) ethanol and 11.3 parts of a Sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 3.7 parts of aqueous ethanol.

example 15th

Following a similar procedure as in Example 1 except that 0.32 parts jecLock off one from the addition of 1 molecule of ethylene oxide to a mixture of commercially available xylenols

509830/0970

directed product is used instead of component (b) uniform coloring with a good color yield was obtained.

Example 14-

Following a similar process as in Example 1, but this time 0.50 parts of the self-emulsifying agent specified below Oil were used in place of component (b), uniform coloring with excellent color yield obtained. The self-emulsifying one used in this example Oil was prepared as follows: The phenol mixture described in Example 10 was treated with ethylene oxide ethoxylated according to the method described in Example 12. A self-emulsifying oil was made by mixing of 85 parts of the product obtained above and 11.3 parts of the Sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 37 parts of aqueous ethanol.

Example 15

Following a similar procedure to Example 1, this time with but instead of component (b) 1.3 parts of a self-emulsifying one Oil was used, which was obtained by mixing 25 parts of 2- (2,3,5-trimethylphenoxy) ethanol, 67.5 parts of isopropanol and 5 »7 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 1.9 parts of aqueous "Ethanol was made of an even color

€ 09830/0970

obtained with an excellent staining yield.

Example 16

Following a similar procedure to Example 1, wherein this time, however, 0.4 parts of the self-emulsifying agent specified below Oil was used in place of the component (b), uniform coloring with excellent Obtained a color yield which was superior to that obtained using one of 69 parts of 2,4-dichlorophenoxypropanol Existing self-emulsifying oil alone was obtained as the active ingredient. The dyeing aid mixture used in this example was made as follows: In one with a stirrer, one thermometer, one on one

Cool all connected reflux condensers and a gas inlet pipe 107 parts of phenyl salicylate and 1.6 parts of triethylamine were introduced into the flask equipped. The device was flushed with nitrogen at the beginning and during the itoxylation a very slow flow of nitrogen was maintained.

While maintaining a temperature of 165 ° C, 30 parts Ethylene oxide gradually over a period of 150 minutes admitted. The product was distilled and there were 56 Parts of a solid distillate at b.p. 170 to 210 ° C / 0.3 mm collected. The phenyl o- (2-hydroxyethoxy) benzoate was recrystallized from isopropanol.

509830/0970

Analysis: '·

over .: G 69.76 H 5.46
found: 69.81 5.58 " %.

A self-emulsifying oil was made by mixing of 34 · »5 parts of phenyl o ~ (2-hydroxyethoxy) benzoate, 34.5 parts 2,4-dichlorophenoxypropanol, 13 parts isopropanol and 13.5 Parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol *

Example 17

Following a similar procedure as in Example 1, this time with but instead of component (b) Ο, Λ parts of a self-contained one he ends of oil were used by mixing 69 parts of 2- (p-t-butylphenoxy) ethanol, 13 parts of isopropanol and 13.5 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol was produced, uniform coloring was obtained with an excellent color yield.

Example 18

According to a similar procedure as in Example 1, but this time instead of component (b) 0.4 parts of a self-emulsifying Oil were used, which was obtained by mixing 72 parts of 2- (2,6-diisopropylphenoxy) ethanol and 21 parts of the Sodium sulfate ester of a commercially available nonylphenol ethylene

509830/0970

oxide adduct has been prepared in 7 parts of aqueous ethanol uniform coloring was obtained with an excellent color yield.

Example 19

After a similar Yerfahren as in Example 1, this time instead of component (b) 0.6 parts of a self-emulsifying one Oil were used by mixing 50 parts of .Diäthylenglykolmono-p-t-butylphenylether with 30 parts of isopropanol and 15 parts of the sodium sulfate ester of a commercially available one Nonylphenol-ethylene oxide adduct in 5 parts of aqueous Ethanol had been produced, a uniform coloration with an excellent color yield was obtained.

Example 20

After a similar procedure as in Example 1, this time but instead of component (b) 0.4 parts of a self-emulsifying one Oil was used, which was obtained by mixing 69 parts of 2- (2-t-butyl-6-methylphenoxy) ethanol and 13 parts of isopropanol and 13.5 parts of the sodium sulfate ester of a commercially available one Nonylphenol-ethylene oxide adduct in 4.5 parts A uniform color was obtained with an excellent color yield.

Example 21

Following a similar procedure to Example 1, this time with

509830/0970

However, instead of the component (b) 0.4 parts of a ^self-: emulsifying oil were used by the. Mixing of 69 parts of 2- (o-lthylphenoxy) ethanol ₁ 13 parts of isopropanol and 13 "5 parts of the Natriumsulfatesters a commercial Honylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol had been established, a uniform color was obtained with an excellent color yield .

Example 22

Following a similar procedure as in Example 1, this time using however, 0.4 part of the self-emulsifiable oil indicated below was used in place of component (b) obtain a uniform coloration with an excellent color yield. The self-emulsifiable used in this example Oil was produced as follows: ■

Into a flask equipped with a stirrer, a thermometer, a reflux condenser connected to a cold trap and a gas inlet pipe, 106 parts of ρ-α, α-dimethylbenzylphenol and 1.6 parts of trietfrylamine were introduced. The apparatus was initially flushed with nitrogen and a very slow nitrogen flow was maintained during the thoxylation. While maintaining the temperature at 17O ⁰ C, 21.8 parts Xtbylenoxidgas were added slowly over a Seitraum of 40 minutes. After cooling, the reaction mixture was dissolved in diisopropyl ether and some solid material was filtered off. The solution was washed with water and

509 8 30/0970

~ ²⁸ "■ ^: 5502154

dried over magnesium sulfate, the diisopropyl ether was distilled, then 96.6 g of 2- (pa, a-dimethyrbensylphenoxy) ethanol were collected at 160 to 170 ° C / 1.8 mm ⁰ C) recrystallized, F. 42 to 43.5 ⁰ C.
Analysis:

Calcd .: C 79.65 H 7.86
found: 79.76 7.62 %.

The self-emulsifiable oil was made by mixing 69 parts of 2- (p-a, a-dimethylbenzylphenoxy) ethanol, 13 parts Isopropanol and 13.5 parts of the sodium sulfate ester of a commercially available one Konylphenol-ethylene oxide adduct in 4.5 parts aqueous ethanol.

Example 23

In a similar procedure to Example 1, except that 0.4 part of the self-emulsifiable oil indicated below was used instead of component (b), a uniform coloration was obtained with a good color yield. The self-emulsifiable oil used in this example was prepared as follows:

In a flask equipped with a stirrer, a thermometer, a reflux condenser connected to a cold trap and a gas inlet tube, 71 parts of 4-chlorine mcresol and 0.5 part of powdered sodium hydroxide were introduced. The apparatus was initially flushed with nitrogen and during

S09830 / 0970

Propoxylation became a very slow stick-off stream maintain. While maintaining the temperature at 140 ° C., 124.2 parts of propylene oxide were added over a period of. Added slowly for 19 hours. After cooling, the product was dissolved in diisopropyl ether until neutral with Washed water, dried over magnesium sulfate. The solvent was distilled off, 172 parts of product remaining, which, as the NMR spectroscopy showed, contained an average of 4 moles of propylene oxide per mole of 4-chloro-m-cresol.

The self-emulsifiable oil was made by mixing 72 parts of the above adduct and 21 parts of a sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 7 parts of aqueous ethanol.

Example 24

Following a similar procedure to Example 1, this time with but instead of component (b) 0.48 part of a self-emulsifiable one Oil was used by mixing 69 parts of 1- (p-a, a-dimethylbenzylphenoxy) propan-2-ol, 13 parts Isopropanol and 1315 parts of the sodium sulfate ester of a commercial nonylphen oil / ethylene oxide adduct in 4.5 parts aqueous ethanol had been produced, a uniform · Coloration obtained with an excellent color yield.

509830/0970

- 50 -

Example 25

• Following a similar procedure as in Example 1, this time with However, 0.48 part of the self-emulsifiable oil indicated below was used in place of component (b) a uniform coloration with an excellent color yield obtained. The self-emulsifiable used in this example oil was made as follows:

In a flask equipped with a stirrer, a dropping funnel, a thermometer, a reflux condenser connected to a cold trap, and a gas inlet tube, 10 7 parts of phenyl salicylate and 2 parts were added. Triethylaiain introduced. The apparatus was initially flushed with nitrogen and a very slow nitrogen flow was maintained during the propoxylation. While the temperature was kept at 160 to 165 ° C., 30 g of propylene oxide were added dropwise over a period of 11 hours. The product was distilled and 76 parts of phenyl o- (hydroxypropoxy) benzoate were collected, b.p. 140 to 150 ° C / 0.4 mm
Analyzes

Calcd .: C 70.58 H 5.92
found: 70.62 6.06%.

The self-emulsifiable oil was prepared by mixing of 75 parts of phenyl o- (hydroxypropoxy) benzoate and 19 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 6 parts of aqueous ethanol

50-9830 / 0970

Example 26

Following a similar procedure as in Example 1, but this time instead of component (b) 0.4 parts of a by mixing 75 parts of 2- (p-cyclohexylphenoxy) ethanol and 19 parts of the sodium sulfate ester of a commercially available one Nonylphenol-ethylene oxide adduct in 6 parts of aqueous ethanol manufactured, self-emulsifiable oil were used, a uniform coloration was obtained with an excellent color yield

Example 27

Using a similar procedure as in Example 1, but this time using 0.08 parts of the self-emulsifiable below Oils were used in place of the component (b), uniform coloration was obtained with an excellent color yield obtain. The self-emulsifiable oil used in this example was made as follows: In one with a stirrer, a thermometer, a reflux condenser connected to a cold trap and a gas inlet pipe equipped flask was 88 parts of p-cyclohexylphenol and 0.5 part powdered sodium hydroxide. The apparatus was initially flushed with nitrogen and during a very slow stream of nitrogen was maintained during the ethoxylation.

While maintaining the temperature at 180 ° C, 52 parts became

S09830 / 0970

Add ethylene oxide slowly over a period of 50 minutes. The product was dissolved in chloroform and the alkali was washed out with water. After drying, the solution was distilled. The diethylene glycol mono-p-cyclohexylphenyl ether distilled over at 170 to 180 ° C./0.01 mm and was obtained in a yield of 100.8 parts.

The self-emulsifiable oil was made by mixing 75 parts of diethylene glycol mono-p-cyclohexylphenyl ether and 19 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 6 parts of aqueous ethanol.

Example 28

Tray a similar procedure as in Example 1, but this time but instead of component (b) 0.48 part of a 2- (styrylphenoxy) ethanols mixed by mixing 69 parts, 13. Parts of isopropanol and 13 * 5 parts of the sodium sulfate ester a commercial nonylphenol-ethylene oxide adduct in 4-, 5 Parts of aqueous ethanol produced> self-emulsifiable oil were used, uniform coloring was obtained with an excellent color yield.

509830/0970

Example 29

Following a similar procedure to Example 1, wherein this time, however, 0.4 parts of the self-emulsifiable material given below Oil were used in place of component (b): a uniform coloration was obtained with an excellent color yield. The one used in this example self-emulsifiable oil was made as follows:, 10 parts of o- (2-hydroxyethoxy) benzoic acid lactone and 0.1 part Lithium amide were submerged in 50 ml of benzyl alcohol for 10 hours Refluxed. The benzyl alcohol was then placed under vacuum distilled off. Chloroform was added and the lithium amide was filtered off on the pump. The product was distilled and 10.8 parts of benzyl o- (2-hydroxyethoxy) benzoate were collected at 150 to 200 ° C / 0.2 mm Analysis; .

calc .: C 7.0.58 H 5.92
found: 70.38 5.90%.

The self-emulsifiable oil was prepared by mixing of 25 parts of benzyl o- (2-hydroxyethoxy) benzoate, 60 parts Isopropanol, 11.2 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 3 »8 parts aqueous ethanol. ,,

Example 30

Following a similar procedure to Example 1, this time with

SO 9 830/0970

but instead of component (b) 0.4 parts of a through Mixing 69 parts of monoethoxylated commercial benzyl cresol, 13 parts of isopropanol and 13.5 parts of the sodium sulfate ester a commercial Nbnylphenol-Äthylenoxid-Ä'ddukts self-emulsifiable oil prepared in 4.5 parts of aqueous ethanol was used, became a uniform Coloration obtained with an excellent color yield.

Example 31

Following a similar procedure to Example 1, this time with however, 0.4 part of the self-emulsifiable oil indicated below was used in place of the component (b), became a uniform coloring obtained with a good color yield. The self-emulsifiable oil used in this example was manufactured as follows:

854 parts of p-lthylphenol were ethoxylated using 7 parts of sodium hydroxide as a catalyst at 145 ⁰ C by a similar method as it has been applied in Example 12, 348 parts Ithylenoxid to form 98? «Deilen 2- (p-ethylphenoxy) ethanol, mp 48 to 49 ° C · Analysis:.

calc .: 0 72.26 H 8.49 found: 72.26 8.57 %.

The self-emulsifiable oil was prepared by mixing of 69 parts of 2- (p-ethylphenoxy) ethanol, 13 parts of isopropanol and 13.5 parts of the sodium sulfate ester of a commercially available one

509830/0970

Nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol.

Example 32

Following a similar procedure as in Example 1, but this time using 0.6 parts of the self-emulsifiable oil specified below instead of component (b),
became a uniform coloration with an excellent one
Parba loot received. The self-emulsifiable oil used in this example was made as follows:
4 to 3.7 parts of 2-Benzyl-4 ~ chlorophenol were prepared using 0.2 parts of sodium hydroxide as a catalyst at 14-5 ⁰ G in a similar manner as in Example 10 with 12.6 parts of propylene oxide propoxylated to give 16.3 Parts 1- (2-benzyl-4- chlorophenoxy) propan-2-ol.

The self-emulsifiable oil was prepared by mixing 50 parts of 1- (2-benzyl-4-chlorophenoxy) propan-2-ol, 35 parts
Isopropanol and 11.25 parts of the sodium sulfate ester
commercial nonylphenol-ethylene oxide adduct in 3.75 parts of aqueous ethanol.

Example 33

Following a similar procedure to Example 1, this time with

509830/0970

"■ 250215A

but instead of component (b) 0.4 parts of a through Mixing 75 parts of 2- (cyclopentylphenoxy) ethanol and 19. Parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct self-emulsifiable oil prepared in 6 parts of aqueous ethanol was used obtain a uniform coloration with an excellent color yield.

Example 34-

In a similar procedure to Example 1, except that 0.4 part of the self-emulsifiable oil indicated below was used in place of component (b), uniform coloring was obtained with excellent color yield. The self-emulsifiable oil used in this example was prepared as follows: 36.8 parts of o-benzylphenol were added using 0.2 parts of sodium hydroxide as a catalyst at 120 ^° C. by a method similar to that in Example 12 with 8.9 parts Ethylene oxide is ethoxylated to form 28.6 parts of 2- (o-benzylphenoxy) ethanol. Analysis:

calc .: 0 78.92 H 7 »06 found: 78.90 7.23 %.

The self-emulsifiable oil was made by mixing 69 parts of 2- (o-benzylphenoxy) ethanol, 13 parts of isopropanol and 13j5 parts of the sodium sulfate ester of a commercially available one

609830/0970

Nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol.

Example 35

Following a similar procedure to Example 1, this time with but instead of component (b) 0.4 part of one obtained by mixing 75 parts of 2- (o-α-methylbenzylphenoxy) ethanol and 19 parts of the sodium sulfate ester of a commercially available nonylphen.ol-ethylene oxide adduct Self-emulsifiable oil prepared in 6 parts of aqueous ethanol was used, became a uniform Coloration obtained with an excellent color yield

Example 56 ; ·

Following a similar procedure to Example 1, this time with but instead of component (b) 0.4 part of one by mixing of 69 parts of 2- (o-allylphenoxy) ethanol, 13 parts of isopropanol and 13.5 parts of the sodium sulfate ester of a commercially available one Nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol produced, self-emulsifiable oil were used obtain a uniform coloring with a good color yield.

example 37

Following a similar procedure to Example 1, with this -r ' times, however, 0.4 parts of the self-emulsifiable given below Oil were used in place of component (b), uniform coloring with excellent coloring was obtained.

509830/0970

- 33 ~

yield obtained. The self-emulsifiable used in this example Oil was produced as follows: 59 »O parts of a mixture of cyclooctylphenols was under Use of 0.3 parts of sodium hydroxide as a catalyst at 145 C by a method similar to that in Example 12 with 13-5 parts of ethylene oxide are athoxylated to give 17-3 Parts of a mixture of 2- (cyclooctylphenoxy) ethanols, Bp. 125 to 150 ° C / O, 8 mm.

I) as self-emulsifiable oil was prepared by blending 69 parts of 2- (Cyclooctylphenoxy) äthanolen, 13 parts of isopropanol and 13 ₅ 5 parts of the Natriumsulfatesters a commercial nonylphenol Jithylenoxid adduct in 4.5 parts of aqueous ethanol.

Example 38 .

Following a similar procedure as in Example 1, except that this time the component (b) instead of 0.4 part of a by mixing 69 parts of 2- (p-1-Methylcyclohexylphenoxy) ethanol, 13 parts of isopropanol and 13.5 parts of a Natriumsulfatesters commercial nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol produced self-emulsifiable oil were used, a uniform color with a very good color yield was obtained.

Example 39

Following a similar procedure to Example 1, this time with but 0.4 parts of the self-emulsifying

509830/0970

oil were used instead of component (b) get a uniform coloring with a very good color yield. The self-emulsifiable used in this example oil was made as follows:

^{63.8 parts of the phenol mixture described in Example 10 were heated to 140 °} C. for 3 hours with 60.0 parts of styrene oxide containing 0.4 part of sodium hydroxide as a catalyst. After dissolving the product in diisopropyl ether, the solution was washed until neutral. The product was distilled and 65 parts of the styrene oxide adduct were obtained, boiling point 120 ° to 180 ° C./0.3 mm. -

The self-emulsifiable oil was made by mixing 69 parts of this styrene oxide adduct, 13 parts of isopropanol and 13 »5 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 4.5 parts of aqueous ethanol.

Example 40 ·. .

Following a similar procedure to Example 1, this time with but instead of component (b) 0.4 parts of a self-emulsifiable one Oil made by mixing 85 parts of 2- (2-isopropyl-4-chlorophenoxy) ethanol and 11.2 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 3 »8 parts aqueous ethanol, was used get a uniform coloring with a very good color yield

S09830 / 0970

Example 41

Following a similar procedure to Example 1, this time with but 0.3 part of 2- (4-allyl-2-methoxyphenoxy) ethanol instead of component (b) were used, a uniform coloring with a very good color yield was obtained.

Example 42

Following a similar procedure to Example 1, this time with but 0.6 parts of the self-emulsifiable mentioned below Oil were used in place of component (b), uniform coloring was obtained with an excellent color yield The self-emulsifiable oil used in this example was prepared as follows:

103 parts of 2,6-di-sec-butylphenol were prepared using 0.5 parts of sodium hydroxide as a catalyst at 150 ⁰ C by a similar method as in Example 12 with 29 parts of ethoxylated Ä'thylenoxid under formation of 7 ° parts of 2- ( 2,6-di-sec.-butylphenoxy) ethanol, b.p. 132 to 136 ° C / O, 9 mm.

Analysis:

calc .: 0 76.75 H 10.47

found: .76.65 10.24 %.

The self-emulsifiable oil was made by mixing 50 parts of 2- (2,6-di-sec-butylphenoxy) ethanol, 13 parts of isopropanol and 11.25 parts of the sodium sulfate ester of a commercially available one Nonylphenol-ethylene oxide adduct in 3 »75 parts of aqueous ethanol.

S09830 / 0970

Example 43

According to a similar procedure as in Example 1, but this time instead of component (b) 0.4 ropes of _{a commercially available nonylphenol by mixing 69 parts of 2- (p-0etylphenoxy) ethanol, 13 parts of isopropanol and 13}} 5 parts of the sodium sulfate ester - Ethylene oxide adduct in 4.5 parts of aqueous ethanol produced self-emulsifiable oil were used, a uniform color was obtained with a good color yield.

Example 44

Following a similar procedure to Example 1, this time with but instead of component (b) 0.6 part of a mixture obtained by mixing 50 parts of 2- (heptylphenoxy) ethanol, 35 parts Isopropanol and 11.25 parts of the sodium sulfate ester of a commercially available nonylphenol-ethylene oxide adduct in 375 parts Self-emulsifiable oil prepared with aqueous ethanol was used, a uniform color with a very good color yield obtained.

Comparison examples

When the active ingredients of component (b) in the above

Examples by the same amounts of the following compounds were replaced:

2-phenoxyethanol, 2-cresoxyethanols, p-cresoxypropan-2-ol, Monochlorophenoxyethanols and 3-hienylprppanol, the color yields were worse.

SO983O / O970

Claims (1)

Claims 1. Process for exhaust dyeing of hydrophobic fibers at 110 to 135 ° C with a disperse dye in Presence of an adduct of an average of 1 to 4 moles of ethylene oxide, propylene oxide or styrene oxide or a combination of these oxides with 1 mole of a phenolic compound of the formula R ₂ (D where mean: η is a number .from 1 to 4, Hy · hydrogen, chlorine, a straight (unbranched) or branched one Alkyl group having 1 to 8 carbon atoms, one Alkoxy group having 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, IU is a straight (unbranched) or branched alkyl group with 1 to 8 carbon atoms, an alkenyl group with 2 to carbon atoms, an Oycloalkylgruppe with 5 to 8 carbon atoms, possibly by one or more. Substituted alkyl groups with 1 to 4 carbon atoms 509830/0976 can be a cycloalkenyl group with 5 "to 8 carbon atoms, an aralkyl group with 7 *> is 9 carbon atoms, which can optionally be substituted by an alkyl group with 1" to 4 carbon atoms, an aralkenyl group with 2 to 5 carbon atoms in the Alkenyirest, a hydroxymethyl or GOOE ₇ group, in which E, .Phenyl, which is optionally substituted by alkyl having 1 to 4 carbon atoms, aryloxyalkyl, in which the alkyl radical contains 2 or 3 carbon atoms and the aryl radical is optionally by a. . or more chlorine atoms or one or more straight (unbranched) or branched alkyl groups having 1 to 4 carbon atoms, or an aralkyl group having 7 to 9 carbon atoms, or a phenylhydroxyethyl group, with the proviso that a) the total number of carbon atoms in (H ^) _n _ ^ j does not exceed 8, t ») if η = 1 and E ₂ = alkyl, the alkyl group contains at least two carbon atoms, and c) if the adduct is derived from styrene oxide, E ^ hydrogen or chlorine. 2. The method according to claim 1, characterized in that an adduct is used, which by condensation of an average of 1 mole of ethylene oxide, propylene oxide, styrene oxide or a combination of these oxides with 1 mole of the compound of the formula (1) given in claim 1 has been prepared. 509830/0970 3. Process according to claim 1 or 2, characterized in that an adduct is used which has been prepared by condensing Λ mol of ethylene oxide with 1 mol of the compound of the formula (1) given in claim 1. 4. The method according to any one of claims Λ to 3 »characterized in that in formula (1) E ^ and / or E2 denote alkyl groups with 1 to 4 carbon atoms (denotes). 5. Process according to one of Claims 1 to 3 »characterized in that in formula (1) Ry denotes an alkoxy group with 1 to 4 carbon atoms. 6. The method according to any one of claims 1 to 3, characterized in that that in formula (1) E ^ and / or E £ alkenyl groups with 3 or 4 carbon atoms mean (means). 7. Process according to Claim 1, characterized in that an adduct of the formula is used as the dyeing aid O- {CH -CH-O- ^ - H yy ^m (2) X ₂ where ILj and η have the meanings given in claim 1, E ^ a straight (unbranched) or branched alkyl group with at most 8 carbon atoms, an alkenyl group with 2 to S09830 / 097Ö Carbon atoms, a cycloalkyl group with 5 Ms 8 carbon atoms, which may optionally contain one or two alkyl groups with 1 to 4 carbon atoms, a cycloalkenyl group with 5 to 8 carbon atoms, a phenylalkyl group with 1 to 3 carbon atoms in the alkyl radical, the optionally may be substituted by alkyl with 1 to Λ carbon atoms in the benzene nucleus, a phenylalkenyl group with 2 to 3 carbon atoms in the alkenyl radical or a hydroxymethyl group, one of the radicals X ^ and Xp is hydrogen, methyl or phenyl and the other is hydrogen and m is is a number from 1 to 4, with the proviso that a) the total number of carbon atoms in (R ^) _ ,, at most 8 is, '; b) λνβηη η = 1 and R ₂ , = alkyl, the alkyl group contains at least 2 carbon atoms, and c) if one of the radicals X _x , and X ^ is phenyl, R ^, can also be hydrogen or chlorine. . 8. The method according to claim 7 »characterized in that in the formula (2) R * and R ₂ ^ are straight (unbranched) or branched alkyl groups with a total of 3 to 7 carbon atoms. 9. Method according to claim 8, characterized in that η denotes the number 1 in formula (2). 10. The method according to claim 7, characterized in that 509830/0970 in formula (2) R ,, hydrogen, methyl or chlorine, η the Number 2 and R ^, cyclopentyl, cyclohexyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl "mean. 11. The method according to claim 7 »characterized in that in the formula (2) R ^, and R ₁ , independently of one another hydrogen or chlorine, one of the radicals X ^ and X ~ phenyl and the other hydrogen, m is the number 1 or 2 and η is a number from 2 to 4-. 12. Process according to Claim 1, characterized in that an adduct of the formula is used as the dyeing aid -CH-O _t H I COOR ₃ where R ^ _f R? and η have the meanings given in claim 1 and X ^, Xp and m have the meanings given in claim 7. 15 · The method according to claim 12, characterized in that in formula (3) R ^ hydrogen, R, phenyl or benzyl, one the radicals X, * and Xo are hydrogen or methyl and the other Hydrogen and m is the number 1. 14-, method according to any one of the preceding claims, characterized characterized in that the hydrophobic fiber is a poly 509830/0070 Ethylene terephthalate fiber is used. . ' 15 »Process according to one of the preceding claims, characterized in that the adduct defined in claim 1 is used in the aqueous dye liquor in an amount of 0.05 to 2 % by volume, based on the total volume of the aqueous dye liquor. 16. The method according to claim 15, characterized in that the adduct used in claim 1 in the aqueous dye liquor in an amount of 0.1 to 1 vol .-%, based on the Total volume of the aqueous dye liquor used. 17 · Method according to one of the preceding claims, characterized in characterized in that the adduct defined in claim 1 with an emulsifying agent and optionally an organic one Solvent mixes to form a homogeneous, self-emulsifiable product * 18. The method according to claim 17, characterized in that a sulfated alkylphenol-ethylene oxide adduct is used as the emulsifier used. 19 · The method according to claim I7, characterized in that a sulfited fish oil is used as an emulsifier, 20 · Hydrophobic fiber, characterized in that it has been dyed according to the method according to one of the preceding claims. - ⁼ "~~ 509830/0970