DE2239930A1 - METHOD OF COLORING POLYESTER FIBERS - Google Patents

Description

The present invention relates to a method for dyeing polyester fibers,

In British Patent No. 1,021,806 there is one Preparation for coloring hydrophobic materials, such as polyester fibers, described which contain an acetate dye Aryl glycol ethers of the general formula

Ar (OCH ₂ CHR) _n OH

where R is hydrogen or methyl, Ar is an aromatic hydrocarbon residue of the benzene series and η - 1 or 2 = · and contains a di- or trichlorobenzene.

In German Patent No. 1,001,966 is a. Process for dyeing and printing textiles made from high-melting polyesters described in which disperse or developing dyes are used in the presence of an oxyalkyl ether from the phenol of the general formula

HO-CH ₂ -CH ₂ -OC ₆ H ₄ -X

wherein the substituent X is hydrogen or methyl or halogen

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means used.

It has now surprisingly been found that in one method for dyeing polyester fibers with disperse dyes in the presence of certain oxyalkyl ethers of di-, tri-, tetra- or Pentachlorophenols or mixtures thereof, the use of a dioder Trichlorobenzene is unnecessary and the color yield of that with oxyalkyl ethers of phenol as described in German Patent No. 1,001,966 is superior.

The present invention relates to a method in which Polyester fibers dyed using an aqueous dye liquor , these being a disperse dye and a compound or a mixture of compounds of the general formula

0-f R'04- H m

where η is an integer from 2 to 5, R 'is an ethylene or isopropylene radical and m has an average value of at most 3, the dye liquor being free from di- or trichlorobenzene. When R 'is an ethylene radical, the adduct of the chlorinated phenol is a primary alcohol and when R' is an isopropylene radical, the adduct of the chlorinated phenol can be a primary or secondary alcohol. Therefore, when a single compound is used in this procedure, m = 1, 2, or 3. However, when a mixture of compounds is used in this process, the value of m for the individual components can be 1, 2 or 3 or even more, provided that the average value of m in the mixture is not greater than three. When m ^{s is} 2 or more, the R 'groups in the molecule may be the same or different. The compound of the formula I can therefore be used as an adduct of a di-, tri-, tetra- or pentachlorophenol with either an ethylene oxide or a propylene oxide or a mixture of these.

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be spoken. The adduct one formed from propylene oxide chlorinated phenol is generally a secondary alcohol, but smaller amounts of the isomeric primary alcohol, may be present. .

If the average value of m is greater than 3, the color yield obtained is no better than that obtained using known compounds in which η = O or 1, for example with phenoxyethanol or monochlorophenoxyethanol . ^; ■. ■ ■. . ■ ·

The method according to the invention is particularly applicable on polyester fibers, the linear high molecular weight esters of aromatic polycarboxylic acids with polyfunctional alcohols, for Example materials made from terephthalic acid and ethylene glycol or dimethylolcyclohexane, and mixed polymers from terephthalic acid and isophthalic acid and ethylene glycol.

Suitable disperse dyes which can be used according to the invention are organic dyes with the Mas.sgabe that they only have limited solubility in water. These dyes can belong to the most varied types of dyes. You can, for example, azo, especially monoazo, and disazo, anthraquinone, Nitro- ^ methine-, styrene-, azostyrene-, nitroacridone- ,. Coumarin, naphthoperinone, quinophthalone or naphthoquinone imine dyes be. ,,

The amount of dye that is used in the dye liquor will depend on the circumstances and can be up to 10% by weight, based on the weight of the fiber to be dyed.

Specific compounds of the formula I which are valuable according to this invention are 2,4-dichlorophenoxyethanol, 2-, 4,5-trichlorophenoxyethanol, 2,4,6rTrichlorphen.oxyatha.npl, 1- (2,4-dichlorophenoxy) -propan-2-ol, 2,6-dichlorophenoxyethanol, pentachlorophenoxyethane pl and 1- (2,4-Dichlorxjhenoxy) -propane-Iro.l. Mixtures of these Connections can also be used. '

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The compounds of the formula I can be added directly to the dyebath or they can be mixed with an emulsifier or a Protective colloid can be formulated. These methods are known to the person skilled in the art. For example, the compounds of formula I with an emulsifier such as a sulfated alkylphenol-ethylene oxide adduct and optionally an organic solvent such as isopropanol to form a homogeneous, self-emulsifiable one Product can be mixed, which can be added to the dye bath. It can also be the product of formula I with a Protective colloid, such as casein, can be formulated and added to the dye bath in this form.

Particularly good results are obtained when a self-emulsifiable oil, which contains 20 to 80% of a product of the general formula I, preferably 60 to 80% 1- (2,4-dichlorophenoxy) propan-2-ol, 5 to 1570 emulsifier, for Example, the sodium salt of nonylphenol-polyethylene glycol ether sulfate (with a content of 20 ethylene oxide units), 10 to 70% organic solvent, preferably 10 to 207 _o isopropanol and 1 to 107 _{o of} water can be used as a dyeing aid.

The process according to the invention can be carried out in batches and the compound of the general formula I can then be added directly to a dyebath. The temperature at which the dyeing is carried out will normally be in the range of 95 to 140 ° C; within this range, low-temperature dyeing processes or high-temperature dyeing processes can be carried out. The low-temperature dyeing process at 95 ° C to the boiling point of the mixture at atmospheric pressure and the HochLemperatur dyeing process can in an overlying temperature up to 140 ⁰ C, for example in the temperature range of 115 carried out to 135 ⁰ C. The duration of the staining will depend on the circumstances, but generally 1 to 2 hours will suffice. The Ver-

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The ratio of dye liquor to fabric should be 3 to 50 parts by volume 1 part by weight, but 10 to 20 parts by volume

to 1 part by weight are preferred.

The amount of the compound of the formula I in the aqueous dye liquor in a process carried out in batches is used, can be in the range of 0.01 to 1% and is preferably in the range of 0.1 to 0.2 percent by volume, based on the Total volume of the aqueous dye liquor.

The dyeing can, if desired, be terminated by transferring the fibers to a separate bath where they are one Reduction clarification process to remove the on the surface adhering dye are subjected. The fibers can then be rinsed and dried. This additional level of The dyeing process is, however, generally according to the invention because of the high yields obtained and the solubilizing effect Dyeing aid not required.

It can also use the process of the present invention continuously as in processes are carried out in which the fibers are impregnated with the dye liquor and then treated with steam such as carpet printing. In such processes, the steam treatment is expediently carried out at pressures performed that are not significantly above atmospheric drude are, and to ensure a reasonable production speed while keeping the damper on a reasonable one Holds large, the steaming time is usually up limited to about 10 minutes.

If polyester fibers in the form of tops, yarns, woven fabrics or carpets with a .Farbflotte, the disperse dyes and contains water, impregnated and then steamed, for example for 10 minutes, only a small proportion of the dye will be used fixed and during the washing after the steam treatment, a large proportion of the absorbed dye is removed, which leads to a low color yield on the polyester fiber and one

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leads to serious contamination of the washing solutions. However, if the dye liquor disperse dyes, water and a small proportion of one of the color auxiliaries according to the invention, the dye fixation is significantly improved, the color yield increased on the substrate and the contamination of the washing liquors correspondingly reduced.

The amount of the compound of general formula I, which is used in the aqueous dye liquor in a continuous process, can be in the range from 0.1 to 5% in emulsified or colloidal form, preferably 0.2 to 4 percent by weight, based on the total weight of the aqueous dye liquor.

The dyeing process of the present invention is particularly valuable when modern high temperature dyeing machines such as DUsen, Reel or pack dyeing machines are used and the resulting dyed material has been found to be free of stains is, a better leveling effect and higher color yield as if no coloring aid is used.

Polyester fibers contain oligomers which escape through the surface of the fibers if the dyeing is carried out at too high temperatures. When the polyester fibers in the presence of compounds of the general formula I, particularly in the absence of added emulsifiers and / or surfactants are colored, the temperatures can be lowered, for example, 10 ⁰ C, to obtain a color yield, which is the equivalent to Monochlorphenoxyäthanolen . This reduces the problems associated with the deposition of the oligomer on the surface of the fibers. In general, the advantages of the process according to the invention are that

1) the dyed polyester fibers have improved rub fastness have and

2) fewer problems with oligomer formation occur - those colored when the compounds of general formula I are present Polyester fibers have better spinning properties. It can therefore

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loose material can be dyed satisfactorily in this manner -

3) further improved leveling properties and better coverage in the case of yarn deviations, as well as high color yield will and

4) the fact that this high yield even at high concentrations of the dye is obtained. The dyeing process is suitable for use with loose material, yarn, woven or knitted fabrics and carpets.

Furthermore, the dyeing method of the present invention can also be used in addition to the fibers made entirely of polyester Mixtures that contain polyester fibers together with other fibers such as wool, cotton, acrylic, cellulose or polyamide fibers, be performed.

In the illustrative examples below, parts and percentages are by weight unless that this is indicated otherwise, with the parts by weight to the Parts by volume have the same ratio as kilograms to liters.

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example 1

4 parts of Crimplene fabric were added to 160 parts by volume of aqueous Dye liquor immersed with the content of a) 0.12 parts of the dye from a mixture of

SO ₂ NHCH ₂ CH ₂ OH

- ν

in a ratio of 1: 1, and

b) 0.32 parts of 2,4-dichlorophenoxyethanol, the pH being adjusted to 5 to 6 with acetic acid.

The dyeing was carried out at a temperature of 120 ^° C. for one hour.

The tissue was then transferred into a separate bath containing 160 parts of x ^ ässrigen Farbliquor containing 0.8 parts of sodium hydroxide solution 70 ° IV, 0.32 parts of sodium dithionite and 0.32 parts of a Aethylenoxydkondensai: s containing from Stearyldiäthylentriamin and at 70 ⁰ Leave C for 30 minutes. The fabric was then rinsed in warm water and dried. A red coloration was obtained with an excellent color yield with the effect of good leveling.

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Example 2

The procedure described in Example 1 was repeated, using 0.12 parts of a mixture of as the dye mixture

Cl OCH ₃

NO ₂ - \ / -. N = N - / V- N

~~ \ / ~~ ^ CH ₉ CH ₉ OCOCHo NO ₂ NHCOCH ^J

NO ₀ - / \ - N = N

/ ^ CH ₉ CHoOCOCH,

NHCOCH ₃

used in a ratio of 3: 1. A navy blue dyeing with excellent color yield and good leveling was obtained effect.

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Example 3 '■■■ -: _

A self-emulsifiable oil was made by 69 parts of 1- (2,4-dichlorophenoxy) propan-2-ol, 13 parts of isopropanol, 13.5 parts of sodium sulfonate ester of a commercially available alkylphenol / ethylene oxide adduct and 4.5 parts of water mixes.

Following a similar procedure to that described in Example 2, but using 0.32 parts of that described above self-emulsifiable oil instead of component (b) you get an excellent color yield with a good leveling effect.

Example 4

Following a similar procedure as described in Example 1, but using 0.16 parts of component (b), excellent color yield was obtained.

Example 5

Following a procedure similar to that described in Example 2, but using 0.16 parts of component (b) you get an excellent color yield.

Examples 6 to 10

Using a method similar to that described in Examples 1 to 5, however, the step in which the tissue was subjected to a reduction clarification process was omitted you get an excellent color yield with a good leveling effect.

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Example 11

Using a method similar to that described in Example 1, but using 0.32 parts of 2,4,6-trichlorophenoxyethanol instead of component (b), an excellent color yield with a good leveling effect was obtained.

Example 12

Following a similar procedure to that described in Example 2, but using 0.32 parts of 2,4,6-trichlorophenoxyethanol instead of component (b), an excellent color yield with a good leveling effect was obtained.

Example 13

Following a similar procedure to that described in Example 1, but using 0.32 parts of 2,4,5-trichlorophenoxyethanol instead of component (b), an excellent color yield with a good leveling effect was obtained.

Example 14

Following a similar procedure to that described in Example 1, but using 0.32 parts of 1- (2,4-dichlorophenoxy) propan-2-ol instead of component (b), an excellent color yield with a good leveling effect was obtained.

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Example 15

Following a similar procedure to that described in Example 1, but using 0.32 parts of a mixture of 2,4-dichlorophenoxyethanol and 2,4,6-trichlorophenoxyethanol in the ratio of 3: 1 an excellent color yield with a good leveling effect was obtained.

, Example 16

By a similar procedure to that described in Example 1, but using 0.32 parts of 2,6-dichlorophenoxyethanol instead of component (b), an excellent color yield with a good leveling effect was obtained.

Example 17

4 parts of Crimplene fabric were in 160 parts by volume of a aqueous solution immersed in the

a) 0.12 parts of the dye, x ^ ie used in Example 1, and

b) 0.64 parts by volume of 1- (2,4-dichlorophenoxy) -propane-2-bl in colloidal Form contained.

The pH of the dyebath was adjusted to 5 to 6 with acetic acid and the dyeing at a temperature of 100 ° C during Carried out for 2 hours. The fabric was then placed in a separate bath and post-treated as indicated in Example 1. Man received an excellent color yield with a good leveling effect ,

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Example 18

18 parts Milchcaseinpulver were dissolved in 77 parts of water at 65 ⁰ C, and thereto 3.6 parts of ammonia (SG 0.880) and 0.46 parts of a 30% aqueous solution of Tetranatriumäthylendiamintetraacetat then added. The temperature was then set to 40 to 50 ^° C. and the mixture was diluted with 50 parts of water. With vigorous stirring, it was then treated with 300 parts of 1- (2,4-dichlorophenoxy) propan-2-ol, which were gradually added, the temperature being allowed to drop to 30 to 35 ^° C. during this time . The reaction mixture was then treated with 65 parts of water and stirred to a uniform consistency. The procedure described in Example 17 was repeated using 0.64 parts of this product in place of component (b). An excellent color yield with a good leveling effect was obtained.

Example 19

Using a method similar to that described in Example 1, but using 0.16 parts of an adduct consisting of 163 parts of 2,4-dichlorophenol and 48 parts of propylene oxide and thereafter was prepared from 18 parts of ethylene oxide instead of component (b), an excellent color yield with good color was obtained Equalizing effect.

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Example 20

A self-emulsifiable oil was made by mixing 40 parts an adduct, which was prepared from 163 parts of 2,4-dichlorophenol and 48 parts of propylene oxide and then 18 parts of ethylene oxide, with 28 parts of isopropanol, 9 parts of sodium sulfonate ester of a commercially available alkylphenol / ethylene oxide adduct and 3 parts Waser prepared.

Following a similar procedure to that described in Example 1, but using 0.32 parts of that described above self-emulsifiable oils instead of component (b), an excellent color yield with a good leveling effect was obtained,

Example 21

Following a similar procedure to that described in Example 17, but using 0.64 parts by volume of an adduct 163 parts of 2,4-dichlorophenol and 48 parts of propylene oxide and then 18 parts of ethylene oxide in colloidal form instead of the component (b), an excellent color yield with a good leveling effect was obtained.

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Example 22

A self-emulsifiable oil was produced by 20 parts of pentachlorophenoxyethanol, 54 parts of isopropanol and 4.5 parts of sodium sulfate ester of a commercially available Nony1-phenol / Aethylenoxydaddaktes mix in 1.5 parts of water.

According to a similar process as described in Example 1, except that the aqueous dye liquor is heated at 80.degree 0.12 part of the dye of the formula

0 NH - (' ^N h -OSO ₂ CH ₃

instead of component (a) and 0.32 part of the above adding self-emulsifiable OeIs instead of component (b), a violet coloration was obtained with an excellent color yield and a good leveling effect.

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Example 23

A paint impregnation liquor became out

a) 1 part of the dye mixture from Example 1,

b) 5 parts of 80% acetic acid,

c) 0.4 parts of carob gum ether and

d) 2 parts of 1- (2,4-dichlorophenoxy) propan-2-ol prepared and made up to 100 parts with water.

A carpet with a pile made of polyester fibers was impregnated with this dye solution by running the carpet through the dye bath left and then maintained in a vertical position until the excess The dyebath had run out, giving a build-up of 450% calculated based on the fiber weight. The impregnated Carpet was then steamed in saturated steam at atmospheric pressure for 10 minutes and washed thoroughly with cold water and dried. The carpet has been dyed with a strong red tint.

Example 24

Similar good results were obtained when component (b) of Example 23 was replaced by 2 parts of a self-emulsifiable oil from 69% 1- (2,4-dichlorophenoxy) propan-2-ol, 13% isopropanol, 12.6% sodium salt of nonylphenol polyethylene glycol ether sulfate (content 20 ethylene oxide units) and 5.4% water was replaced.

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Comparative example A

A similar process to that described in Example 1, but without component (b), gave a coloration that was not had good color yield or good leveling effect.

Comparative example B

Following a similar procedure to that described in Example 17, but using o- and p-monochlorophenoxyethanols in colloidal form instead of component (b), the color obtained by the coloring was comparatively weak.

Comparative Example C

Following a similar procedure to that described in Example 1, but using a mixture of o- and p-monochlorophenoxyethanols instead of component (b), the coloring provided "a comparatively faint" color.

Comparative Example · D

Following a similar procedure to that described in Example 1, but using 0.64 parts of p-bromophenoxyethanol instead of component (b), a coloration was obtained which did not produce a good color yield exhibited.

Comparative example E.

Following a similar procedure to that described in Example 1, but using phenoxyethanol instead of the component (b), the color yield of the dyeing was even lower than in Comparative Example C.

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Claims (12)

Claims 1. Process for coloring textile fiber material made of polyester with an aqueous dye liquor containing a disperse dye, characterized in that the dye liquor as Dyeing auxiliaries a compound or a mixture of compounds the general formula 0 (R ¹ O) H where η is an integer from 2 to 5, R 'is an ethylene or isopropylene radical and m has an average value of at most 3 and if m is greater than 1, R ^{1 can be} identical or different. 2. The method according to claim 1, characterized in that a compound of the formula I is used in which m = 1 and η and R ^{1 have} the meanings given in claim 1. 3. The method according to claim 2, characterized in that a compound of the formula I is used in which m - 1, η = 2 and R ^{1 has} the meaning given in claim 1. 4. The method according to claim 2, characterized in that the compound of formula I is 2,4,5-.Trichlorphenoxyethanol, 2,4,6-trichlorophenoxyethanol or pentachlorophenoxyethanol are used. 5. The method according to claim 3, characterized in that as a compound of formula I 2,4-dichlorophenoxyethanol, 1- (2,4-dichlorophenoxy) -prppan-2-ol or 2,6-dichlorophenoxyethanol is used. 30982W 1034 .- 19 - ■ ■. 6. The method according to any one of claims 1 to 5, characterized characterized in that the polyester fiber material used is polyethylene glycol terephthalate is. 7. The method according to any one of claims 1 to 6, characterized in that that the compound of the formula I is mixed with an emulsifier or protective colloid before it is added to the dyebath. 8. The method according to claim 7, characterized in that a dyebath is used which contains a self-emulsifiable oil as a color auxiliary, which consists of 20 to 80% of a product of the formula I according to claim 1, 10 to 707o organic solvent, 5 to 157o emulsifier and 1 to 107 _{o is} water. 9. Process carried out in batches according to one of the claims 1 to 8, characterized in that the compound of the formula I is obtained in an amount of 0.01 to 1 percent by volume based on the total volume of the aqueous dyebath. 10. The method according to any one of claims 1 to 9, characterized in that that the dyeing is carried out at a temperature of 95 to 140 ° C. 11. Continuous process according to one of claims 1 to 10, characterized in that one is the compound of the general Formula I used in an amount of 0.1 to 5 percent by weight, based on the total weight of the aqueous liquor. . 12. The colored according to the method according to claims 1 to 11 Polyester fiber material. · * ■ 309824/1034