DE2146761A1 - Process for the production of lightfast colors and prints on synthetic fibers - Google Patents

Description

2H6761

FARBWERKE HOECHST AG formerly Master Lucius & Brüning

HOE 71 / F242 Dr, Cz / vo

Process for the production of lightfast dyeings and prints

synthetic fibers

For dyeing polyester fibers with disperse dyes, there are four following from the practical point of view basic options available:

a) dyeing in an aqueous medium by the exhaustion method at boiling temperature with the addition of a carrier, the aid acting as a fiber "opener". This results in a considerable increase the color yield.

b) dyeing by the pull-out method under HT conditions at 120 bis

140 ^° C., optionally with the addition of a carrier, the function of the carrier is to be sought mainly in its equalizing properties; dyeing under HT conditions also includes that for polyester-wool blends
with reduced carrier addition.

the usual dyeing for polyester-wool blends at 105-106 ° C

c) dyeing by the so-called "thermosol process" or a Steaming process, whereby the working stroke is mechanical, even Application of the dyes to the textile materials and fixation of the dyes by means of a heat treatment (dry heat and / or. Steam).

d) dyeing from organic solvents according to a continuous or discontinuous procedure, with uniform solvents, Solvent mixtures (also azeotropic) or solvent / water emulsions can be used in which the dyes be in dissolved or dispersed form.

It is in connection with the variants shown above for the production of polyester dyeings known to the person skilled in the art that

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when dyeing with the addition of a carrier, the lightfastness of the dyeings deteriorates in many cases if Carrier residues remain in the fiber, although in such cases different types of carrier behave quite differently. The carrier systems mainly used in practice today are based on the following chemical compounds as effective carrier components based on:

1) aromatic carboxylic acid esters,

2) chlorinated, aromatic hydrocarbons,

3) Phenol derivatives and diphenyl, as well

4) naphthalene derivatives.

The carrier substances listed in groups 1) and 2), such as methyl benzoate, methyl salicylate, Mono-, di- and trichlorobenzenes or -toluenes, etc., do not influence the lightfastness of dyeings or can be easily removed Treatments, such as drying in the air or at temperatures that correspond to drying temperatures customary in practice, remove from the fiber again. Disadvantages for these types of carrier compared to groups 3) and 4) are theirs strong water vapor volatility (carrier stains) in the In most cases, there is a stronger odor nuisance and that which is present in the case of the chlorinated, aromatic hydrocarbons is very strong Toxicity.

The carriers summarized in groups 3) and 4) are the main ones based on diphenyl, 2-hydroxydiphenyl and methylnaphthalenes built up. With regard to the influence on light fastness, diphenyl is one of these three carrier substances by far the best. Through a light heat treatment, for example at the drying temperatures customary in practice, the residues of diphenyl remaining in the fiber during dyeing can be eliminated to such an extent that yellowing phenomena and thus Deteriorations in the light fastness of dyeings no longer occur. The findings are completely different for the last two compounds mentioned: 2-hydroxydiphenyl and especially methyl naphthalenes can practically only be removed from the fiber by special heat treatment, which does absolutely nothing with the term drying have more in common. In the case of methylnaphthalenes included in this

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Point showing the worst result is an example of this a minimum temperature of 140 C is required, at which the dry goods must be treated for at least 3 minutes, to volatilize the carrier residues to the point that they are impaired the lightfastness of the dyed goods is no longer recognizable. To the practitioner, this fact means that Carriers based on the last-mentioned connections, which, by the way, are very established and widespread in practice, are theirs Have limits and can no longer be used where no such special heat treatment can be carried out, if So, for example, the machine requirements are not met (e.g. when drying muffs) or impairment of the fiber properties can occur (e.g. with textured fibers). In addition, it must not be overlooked that the aforementioned "more severe drying conditions" are not entirely insignificant Mean energy expenditure.

It has now been found that lightfast dyeings and prints that cannot be influenced by dye accelerators on synthetic fiber material, preferably linear polyester fibers, with insoluble dyes, if the dyeings are made in the presence of Organophosphorus compounds of the general formula (1) and / or amine oxides of the general formula (2)

if

ΐ ^ X ^ R, ^t ^ - ^R l

R - VZT (D R- N <" ^λ (2) ^ YR ^

carries out, in which R, R- and R "unbranched or branched, optionally substituted by phenyl, hydroxy, cyano or amino groups or Ilalogenatoms and optionally by oxygen, sulfur and / or nitrogen atoms and / or by a carboxylic acid ester, Carbonamide or a sulfonic arid group denote interrupted alkyl or alkenyl radicals with 1 to 20 carbon atoms, the radicals XR- and YR ₂ or R- and R "being components of a hetercyclic five- or six-membered ring formed together with the central phosphorus or nitrogen atom can, with the proviso that the sum of the _{total carbon atoms contained in R, R 1} and R _{2 is} at least 6 and at most 25, and X and Y are a direct bond imd / or an oxygen atom, or without

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Use of such tools of the formulas (1) and / or (2) The dyeings and prints produced are treated with it and / or after the dyeing or printing of this auxiliary during the subsequent Additive cleaning of the dyed or printed goods.

According to the present invention it is now possible without a Having to fear deterioration in light fastness, carrier substances of the latter types to be used in the dyeing of synthetic fibers, whereby the special post-heat treatment is not necessary ' is when products of the general formulas (1) or (2) are used in the dye bath, in the aftertreatment bath or in the carrier preparation will.

Of the organophosphorus compounds of the formula (1) or amine oxides to be considered according to the present invention Formula (2) include the following products as examples:

Octyl-diraethyl-phosphine oxide, octyl-diethyl-phosphine oxide, decyl-dimethyl-phosphine oxide, Decyl methyl butyl phosphine oxide, dodecyl dimethyl phosphine oxide, Dodecyl diethyl phosphine oxide, \ / - palmitic acid amidomethyl dimethyl phosphine oxide, ^ - palmitic acid amidopropyl dimethylphosphine oxide, Hexyl-methyl-butyl-phosphine oxide, hexyl-dimethylphosphine oxide, Propyl methyl phosphinic acid isobutyl ester, dodecyl methyl phosphinic acid ethyl ester, DodecyI-methyl-phosphinic acid-2-chloroethyl ester, Isobutyl decyl methyl phosphinate, dimethyl octanephosphonate, Octanephosphonic acid diethyl ester, butanephosphonic acid dibutyl ester, hexanephosphonic acid diethyl ester, hexanephosphonic acid di-isobutyl ester, Octyl-dimethyl-amine oxide, N-dodecyl-piperidine-N-oxide, Tetradecyl dimethyl amine oxide, coconut fat dimethyl amine oxide, oleoylamidomethyl dimethyl amine oxide or hexadecyl bis (ß-hydroxyethyl) amine oxide.

For the effectiveness of the above-mentioned phosphine oxides, phosphinic acid esters or phosphonic acid esters of the formula (1) or amine oxides of the formula (2) it is immaterial in connection with the claimed process, whether these are used in an aftertreatment bath, or the dye bath directly or indirectly, i.e. with the addition of a special one Carrier preparation, are added.

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According to the method, for example, the following possible applications are possible given:

Post-treatment of the "carrier" dyeing in an aqueous liquor, which contains 0.5 to 10 g / l, preferably 2 to 5 g / l, of the products mentioned under the general formulas (1) and (2); the Treatment is about 10 to 20 minutes at temperatures between room temperature and cooking temperature, preferably at 50 to 90 ° C, carried out. This post-treatment process can also be carried out simultaneously with the reductive post-cleaning which is customary for polyester dyeings can be combined, i.e. that the indicated auxiliaries either in addition to the alkali, reducing agent and usually also a Detergent-containing reductive post-cleaning bath added or possibly also in the reductive post-cleaning liquor instead the usual detergent can be used.

Another additional option for the organophosphorus mentioned Compounds or amine oxides are added directly to the dye bath, whereby the products can be added from the start of dyeing. however, they are preferably only added to the dyebath when the last third to quarter of the total dyeing time has been reached.

There is yet another variation of the method according to the invention therein to use the stated products of the formulas (1) or (2) first in the carrier preparation, whereby when the with the Auxiliaries produced carriers at the same time an indirect addition of the products into the dye bath takes place.

The commercially available carriers introduced in practice contain small additives (such as stabilizers for the shelf life of the preparation, auxiliaries for improving emulsification, re-emulsification, emulsion resistance, etc.) the following main components:

Carrier-active substance (possibly also mixtures of several carrier-active Substances), emulsifier (mostly mixtures of different egg Emulsifiers) and optionally noca eia dissolving aids. In the case of using carriers that are liquid at room temperature Connections will in most cases rely on the use of a additional solution aid is dispensed with, i.e. the carrier

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Mainly holds the liquid, carrier-active substance and Emulsifiers. In such a case, a carrier preparation can be obtained by simply mixing in the auxiliaries according to the invention the use of which enables the products to be added indirectly to the dye bath. The situation is different when using Carriei'active compounds which are solid at room temperature; here there is also an additional advantage when using the organophosphorus compounds or the amine oxides. Usually Carrier-active substances that are solid at room temperature are in most cases first dissolved in a solvent; after adding Emulsifiers then result in a liquid carrier setting. Of course, there are also some carriers in paste or dough form on the market to be found that have been prepared from solid, carrier-active substances without dissolving aids. Delight with the practitioner However, these carrier preparations are not very popular, since their handling is always associated with greater difficulties than that of liquid carriers (more laborious emulsification, certain minimum temperature of the dyebath before adding the carrier, etc.). By using the products of the general Formulas (1) and (2) it is now possible to use liquid carrier adjustment. .; based on solid carrier compounds at room temperature without the addition of a solubilizing agent in such a way that they have a solid carrier-active substance in approximately the same amount of the above Auxiliaries, possibly by gentle warming, is dissolved and then mixed with an emulsifier. By adding this Carrier adjustments in the dyebath are also achieved, as in the case described above, an indirect addition of the substances according to the invention Recommended products for the dye bath.

The inventive method is suitable for the production of Dyeing and printing on synthetic fiber materials, such as linear polyester, polyamide, polyacrylonitrile or Cellulose triacetate fibers, which are also present in a mixture with one another or in a mixture with natural fibers such as cellulose or wool can. The dyes used for these materials are, for example, disperse, acid and water-insoluble metal complex dyes in question.

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example 1

Polyester staple fiber yarn is treated in a liquor ratio of 1:25 for 90 minutes and at 98 ° to 100 ° C in a dye bath, that - based on the weight of the dry goods -

0.1 % of the dye of the formula

- O- (CH ₂ ) ₆ -OH

O OH

as well as 4 g / l of a commercially available carrier based on methylnaphthalene (with about 60 % effective carrier substance)

on

contains and adjusted the pH value of 5.5 by means of acetic acid is.

In addition, all other things being equal, a "blind" staining without the above-mentioned dye will be on the same Material made.

Both colorations, i.e. the pink coloration obtained in the first case and that in the second case without dye, only with carrier according to the Material treated with the same dyeing conditions are then divided into two identical samples and one sample of each of these dyeings is subjected to a reductive post-cleaning which is customary in polyester dyeing, rinsed and air-dried while the other two swatches can only be rinsed and allowed to air dry.

The 4 samples that are now available are then again divided into several parts, and in each series - in each case in Fleet ratio of 1:20 and in an aqueous fleet - the carried out the following post-treatment processes:

1) 3 g / l decyl dimethyl phosphine oxide, 15 minutes at 85 ° C

2) 3 g / l coconut fat dimethyl iunine oxide, 20 minutes at 80 ^P C

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The two samples not previously reductively cleaned also become ground each after-treated for 20 minutes at 85 ° C with one of the aqueous liquors of the composition given below:

a) 2 g / l decyl dimethyl phosphine oxide, 5 ml / 1 sodium hydroxide solution 32.5%,

2 g / l sodium dithionite, and

1 g / l of a detergent based on an alkylphenol poly-

glycol ethers;

b) 3 g / l decyl dimethyl phosphine oxide, 5 ml / 1 sodium hydroxide solution 32.5%, and

2 g / l sodium dithionite.

All post-treated samples are then rinsed and applied to the Air dried.

Except for the aftertreatment operations described above for dyeings that do not involve the aid of the invention were generated, separate colorations are also produced in accordance with the methods explained at the beginning or treatments of the Material carried out without dye, in these cases 3 g / l decyl-dimethyl-phosphine oxide

a) the dye bath from the start of dyeing,

b) the dye bath after a dyeing time of 1 hour

added. These colorations produced with the addition of the phosphine oxide are then reductively cleaned in the usual way, rinsed and air dried.

All of the samples generated in the above-mentioned manner will then exposed in the Xenotest device. When assessing the lightfastness properties the following differences arise:

All colorations that have not been aftertreated with the phosphine oxides or amine oxides or produced without these substances or the corresponding ones White materials treated without dye show extremely strong signs of yellowing, whereas with all with the auxiliaries post-treated or manufactured samples hardly show any yellowing due to incompletely removed residues of carrier preparations is still visible.

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Example 2

The following carrier settings are first made:

1) 43% o-phenylphenol

43% decyl dimethyl phosphine oxide

14 % of a mixture of 65% dodecylbenzenesulfonate

20% butanol

10% Sinarol-2-sulfamidoacetic acid triethanolamine salt

5 % oleic acid

2) 46% o-phenylphenol

38% decyl dimethyl phosphine oxide

16% of a reaction product of 1 mole of castor oil with 36 moles of ethylene oxide.

Under the usual staining conditions-i - but without use a dye - are now fabric samples made of polyester fibers in a liquor ratio of 1:25 for 1 1/2 hours and at 98 ° up to 100 C treated with aqueous liquors which are adjusted to pH 5.5 with acetic acid and which are in accordance with the corresponding Samples contain the following amounts of carriers - each based on the o-phenylphenol content:

a) 1.8 g / l of that described under 1) at the beginning of this example

Carrier preparation

b) 1.8 g / l of that described under 2) at the beginning of this example

Carrier preparation

c) 1.8 g / l of a commercially available carrier based on o-phenylphenol.

After the "dyeing" has been completed, these are applied in the usual way reductively cleaned, rinsed, air-dried, and - as in Example 1 - in the Xenotest device, according to the usual Type of light fastness test, exposed.

The material treated with the commercially available carrier shows (c) a very strong yellowing during the other two samples (a) and (b) show this phenomenon only to a very small extent. When assessing the strength of this yellowing with the

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"Gray scale" for evaluating the staining (according to ISO Recommendation R 105, according to DIN 54002 and SNV 95806) are level 2 for the sample (c) treated with the commercially available carrier, for the the two other samples (a) and (b) grades 4-5 on the gray scale comparable.

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Claims (13)

- 1--2U6761 claims; 1) Process for the production of lightfast, by means of dye accelerators non-influenceable dyeings and prints on synthetic fiber material, preferably linear polyester fibers, with insoluble dyes, characterized in that the dyeings and prints are carried out in the presence of organophosphorus compounds of the general formula (1) and / or amine oxides of the general formula (2) R-P '(1) R- N ^ (2) carries out, in which R, R ^ and R "unbranched or branched, optionally substituted by phenyl, hydroxy, cyano or amino groups or halogen atoms and optionally by oxygen, sulfur and / or nitrogen atoms and / or by a carboxylic acid ester, Carbonamide or a sulfonamide group denote interrupted alkyl or alkenyl radicals with 1 to 20 carbon atoms, where the radicals XR ₁ and YR ₂ or R and R can be components of a heterocyclic five- or six-membered ring formed together with the central phosphorus or nitrogen atom , with the proviso that the sum of the _{total carbon atoms contained in R, R and R 2 is} at least 6 and at most 25, and X and Y represent a direct bond and / or an oxygen atom, or without the use of such auxiliaries of the formulas (1) and / or (2) dyeings and prints produced therewith aftertreated and / or after dyeing or printing this auxiliary in the subsequent reductive cleaning ng of the dyed or printed goods. 2) Method according to claim 1, characterized in that the organophosphorus compound and / or the amine oxide in the dye bath is used. 3) Method hach claim 1, characterized in that the organophosphorus compound and / or the amine oxide in the printing paste is used. 4) Vex'fahren according to claim 1, characterized in that the Organophosphorus compound and / or the amine oxide in the 3098U / 1U1 / 12- Carrier preparation is used. 5) Method according to claim 1, characterized in that the organophosphorus compound and / or the amine oxide in the aqueous aftertreatment baths is used. 6) Method according to claim 5, characterized in that the Organophosphorus compound and / or the amine oxide is used in the alkaline, reductive cleaning baths. 7) Method according to claim 5, characterized in that the organophosphorus compound and / or the amine oxide in the acidic Post-cleaning baths is used. \ 8) Process according to claims 1-7, characterized in that phosphine oxides, phosphinic esters or phosphonic esters are used as organophosphorus compounds. 9) Method according to claim 8, characterized in that as organophosphorus compounds octyl dimethyl phosphine oxide, Octyl diethyl phosphine oxide, decyl dimethyl phosphine oxide, decylmethyl butyl phosphine oxide, Dodecyl dimethyl phosphine oxide, dodecyl diethyl phosphine oxide, y-palmitic acid amidome 1h yl dimethyl phosphine oxide, y -'- Palraitic acid amidopropyl-diraethyl-phosphine oxide, Hexyl-dimethylphosphine oxide, hexyl-methyl-butyl-phosphine oxide, Propyl methyl phosphinic acid isobutyl ester, dodecyl methyl phosphine k acid ethyl ester, dodecyl methyl phosphinic acid - ^ - chloroethyl ester, Decyl methyl phosphinic acid isobutyl ester, octane phosphonic acid dimethyl ester, Octanephosphonic acid diethy! Ester, butanephosphonic acid dibutyl ester, Hexanephosphonic acid diethyl ester or hexanephosphonic acid di-isobutyl ester or mixtures of these products are used. 10) Process according to claims 1-7, characterized in that the amine oxides octyl-dimethyl-amine oxide, N-dodecyl-piperidine-N-oxide, Tetradecyl dimethyl amine oxide, coconut fat dimethyl amine oxide, oleoylamidomethyl dimethyl amine oxide or hexadecyl bis (ß-hydroxyethyl) amine oxide or mixtures of these products can be used. 309814/1141 11) The according to claims 1-10 dyed or printed textile »Materials. 12) Use of organophosphorus compounds of general Formula (1) and / or amine oxides of the general formula (2) as auxiliaries in dye baths or printing pastes or in post-treatment baths in the production of dyeings and prints according to the process according to one or more of claims 1-10. 13) Use of organophosphorus compounds of general Formula (1) and / or amine oxides of the general formula (2) as dissolving auxiliaries for solid, carrier-active substances in the Production of dyeings and prints according to the method according to one or more of claims 1-10. 30S914 / 1U1