DE2146761C3 - Process for the production of non-fast dyeings on synthetic fibers - Google Patents

Description

common formula (2) dyeing from organic solvents according to a

continuous or discontinuous working

J YR ₁ ¹⁵ wise, whereby uniform solvents, solvent

£ / (1) mixtures (also azeotropic) or solvents /

^K ~ - \ water emulsions can be used,

Y-R, in which the dyes are in solution or in

in dispersed form.

₀ 30 V *

t / ^R > _{ηΛ In} connection with the above

R-Nf ^Kl) shown variants for the generation of poly

\ _R ester dyeings known to the person skilled in the art that with

* Dyeing with the addition of a carrier in many cases

^a5 s \ ne deterioration of light fastness of Fär-

carries out, in which R, R ₁ and R ₁ unbranched ^ J ^ SS if carrier residues in the fiber branched or branched, possibly by phenyl, "ngen * _{η so} , _{chen FäUen then} ^^

Hydroxy, cyano or amino groups or Ha-. J ™;? ^ Carrier types quite different lied atoms substituted and possibly by ~ Γ * Ϊ ~ _The Today hauptsächüch verSauerstoffSchwefel- _{in practice} and / or nitrogen atoms ₃ o Jjjgj water systems based on the following chemical and / or a carboxylic acid ester, carboxylic ^ ™ ^ "^ ₅ \ n _Asum carrier components zuamid- or a suffonamidgruppe interrupted veroinaungcn <w,
Alkyl or alkenyl radicals with 1 to 20 carbon reasons:

atoms mean, where the radicals X - R ₁ and 1) aromatic carboxylic acid esters,
YR ₁ or R ₁ and R ₁ constituents of an added 35 2) chlorinated, aromatic hydrocarbons,
together with the central phosphorus or stick 3) phenol derivatives and diphenyl as well
heterocyclic five or 4) naphthalene derivatives formed by a substance atom.

Can be six-membered, with the proviso that the _v . , » ,, -U ^ r ·, ^: -,

Sum of the total contained in R, R ₁ and R ₁ The <-arner- listed in groups 1) and 2)

Carbon atoms is at least 6 and at most 25 40 substances, such as methyl benzoate, and X and Y are a direct bond and / ester, salicycure methyl ester, mono-, Ui- and l n- or mean an oxygen atom, or without anchlorobenzenes or anchlorobenzenes or -toluenes and the like, influence the turn of light of such aids of the formulas (1) the fastness of dyeings is not or can be passed through and / or (2) colorations produced therewith after simple treatments, such as drying treated and / or after dyeing this auxiliary 45 in the air b * v. at temperatures that are prevalent medium in the aqueous, optionally acidic drying temperatures, again from the Remove subsequent cleaning baths or the subsequent fibers. Carncr reductive cleaning is disadvantageous for this adds to the dyed goods. types compared to groups 3) and 4) their strong ones

2. The method according to claim 1, characterized in water vapor volatility (Carner stains) in the draws that the organophosphorus compound 50 in most cases stronger odor nuisance and the and / or the amine oxide is used in the carrier preparation in the case of the chlorinated, aromatic Konlenwassers will consider substances present very strong toxicity.

The carriers summarized in groups 3) and 4) are mainly based on diphenyl,

55 2-Hydroxydiphenyl and Methylnaphthalenes built up. With regard to the influence on light fastness

Of these three carrier substances, the dye used to dye polyester fibers with dispersion from a practical standpoint, phenyl is by far the best. By a slight considered, the following four basic possible heat treatment, such as in the Handles available: 60 drying temperatures, customary in practice, can be

the residues left in the fiber during dyeing

a) Eliminate dyeing in an aqueous medium after the exhaust diphenyl so far that yellowing disc method at cooking temperature with the addition of a voltage and thus deterioration of the licntecnt carrier, whereby the aid no longer appears as a fiber »opener« in dyeings. Quite works. This results in a considerable increase 65 the finding is different in the case of the latter two the color yield. Compounds: 2-hydroxy-diphenyl and in particular

b) Dyeing by the exhaust method under HT loading methylnaphthalenes can practically only by spezidingungen at 120 to 140 ⁰ C, optionally heat-treatments rush removed from the fiber

, a ,, which have absolutely nothing in common with the term drying. In the case of Methylnaphthadie this point, the worst result this a minimum, for example, "140 ⁰ C is required, in which the" goods have treated at least 3 minutes to the Carrier remains so far as to verflüch- ^ that an impairment of light fastness colored Goods are no longer recognizable For the tiker, this fact means that carriers on the last-mentioned connections, which incidentally are very established and widespread in practice, have limits and can no longer be used where no such special thermal insulation is carried out if the machine requirements are not met in both cases (e.g. when drying muffs) or the fiber properties are impaired

can (ζ. B. with textured fibers). In addition, may It should not be overlooked that the aforementioned "more severe drying conditions" do not make one mean very insignificant expenditure of energy.

It has now been found that the dyeings are lightfast and cannot be influenced by dye accelerators • On synthetic fiber material, preferably linear Polyester fibers can be produced with insoluble dyes if the dyeing is carried out using the exhaust method in the presence of carrier substances as well of organophosphorus compounds of the general formula (1) and / or amine oxides of the general formula (2)

XR ₁

(D to be used, whereby the special post-heat treatment is not necessary if products of the general formulas (1) or (2) are also used in the dyebath, in the aftertreatment bath or in the carrier preparation.

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

ID Octyl-dimethyl-phosphine oxide, Octyl diethyl phosphine oxide, Decyl dimethyl phosphine oxide, Decyl methyl butyl phosphine oxide, dodecyl dimethyl phosphine oxide, Dodecyl diethyl phosphine oxide, y-palmitic acid-amidomethyl-dimethyl-

phosphine oxide, y-phenitic acid amidopropyl dimethyl

phosphine oxide,

Hexyl-methyl-butyl-phosphine oxide, Hexyl dimethyl phosphine oxide, Propyl methyl phosphinic acid isobutyl ester, dodecyl methyl phosphinic acid ethyl ester, Dodecyl methyl phosphinic acid ^ chloroethyl ester, decyl methyl phosphinic acid isobutyl ester, Octanephosphonic acid dimethyl ester, 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, Oleoyl-amidomethyl-dimethyl-amine oxide or hexadecyl-bis-1 / I-hydroxy-ethyl-amine oxide.

35

R »

carries out, in which R, R, and R ₂ 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 sulfonamido group are interrupted alkyl or alkenyl radicals with 1 to 20 carbon atoms, where the radicals X - Ri and Y - R ₂ or R ₁ and R _{2 are} components of a heterocyclic five- or six-membered rings, 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 and / or an oxygen atom, or without the use of auxiliaries of the formulas (1) and / or (2) produced therewith aftertreated and / or after the dyeing of this auxiliary in the subsequent reductive cleaning of the dyed goods clogs.

According to the present invention, it is now mo] you without deterioration in light fastness to have to fear carrier substances of the latter types when dyeing synthetic fibers For the effectiveness of the above-mentioned phosphine oxides, phosphinic acid esters or phosphonic acid esters It is (2) 40 of the formula (1) or amine oxides of the formula (2) In connection with the claimed process, it is immaterial whether this is done in an aftertreatment bath are used or the dyebath directly or indirectly, d. H. with the addition of a special carrier preparation.

According to the method, for example, are the following Possible applications:

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

Another. Additional option for the named Organophosphorus compounds or amine oxides are added directly to the dye bath, whereby the products can be added from the start of dyeing. preferably the dyebath, however, only when it is reached

2148761

the last third to a quarter of the total staining rate be admitted.

Yet another variation of the invention The method consists in initially using the stated products of the formulas (1) or (2) in the -SarrierZ division, whereby when adding 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 ones introduced in practice In addition to 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 emulsifiers) and optionally also a solvent in most cases the use of an additional solvent aid is dispensed with, d. H. the Carrier mainly contains the liquid carrier-active substance and emulsifiers. In one of those 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. Sees differently it in the case of the use of solid carrier-active compounds at room temperature; here occurs also an additional advantage when using the organophosphorus compounds or the amine oxides. Usually at room temperature solid carrier-active substances in most cases initially dissolved in a solvent; after The addition of emulsifiers then results in a liquid carrier setting. On the market are of course some carriers can also be found in paste or dough form, which are made up of solid carrier-active substances' have been prepared without a solvent. These carrier preparations are very popular with practitioners however, it is not very popular, as handling them is always associated with greater difficulties is. than that of the liquid carrier (more complicated emulsification, certain minimum temperature of the dyebath before adding def carriers etc.). Using the products of general formulas (1) and (2) it is now possible to produce liquid carrier settings on the basis of carrier-active compounds which are solid at room temperature without the addition of a solvent in such a way that the most carrier-active substance is in approximately the same amount mentioned auxiliaries, possibly by gentle warming, dissolved and then with an emulsifier is mixed. By adding these carrier settings to the dyebath, one also achieves the same as in previously described case, an indirect addition of the products recommended according to the invention to the dyebath.

The inventive method is suitable for Production of dyeings on synthetic fiber materials, such as linear polyester, Polyamide, polyacrylonitrile or cellulose triacetate fibers, which can also be mixed with one another or in Mixture with natural fibers, such as cellulose or wool, can be present. As dyes for these materials, for. B. disperse, acid and water-insoluble metal complex dyes in question.

example 1 Polyester staple fiber yarn is in the liquor ratio

voji 1:25 for 90 minutes and at 98 to 100 ⁰ C in treated with a dye bath, which - based on the

Weight of dry goods - 0.1% of the dye

the formula

O NH ,,

O - (CH ₂ ), - OH

Ö OH

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

ao substance) and which is adjusted to pH 5.5 with acetic acid

In addition, all other things being equal, there will be a "blind" coloration without the one mentioned above Dye made on the same material

»5 Both dyeings, ie the pink dye obtained in the first case and the material treated in the second case without dye, only with carrier according to the same dyeing conditions, are then divided into two identical samples, and one sample of this dye Exercise becomes a common practice in polyester dyeing Subjected to reductive cleaning, rinsed and air dried while the other two

Samples can only be rinsed and air dried. The now available 4 samples are then

again divided into several parts, and there will be at In each series - in each case in a liquor ratio of 1:20 and in an aqueous liquor - the following post-treatment processes are carried out:

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

2. 3 g / l coconut fat-dimethyl-amine oxide, 20 minutes at 80 ⁰ C.

The two samples that were previously not reductively cleaned are also used for 20 minutes at 85 ° C one of the aqueous liquors of the composition given below after-treated:

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 alkyl

phenol polyglycol 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 air-dried

Except for the post-treatment operations described above for staining, which were carried out without assistance of the auxiliary according to the invention were generated, separate colorations are also according to 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

clogs. These colorations, produced with the addition of the phosphine oxide, are then applied to the usual Wise reductively cleaned, rinsed and air-dried.

All of the samples produced in the above-mentioned manner are then exposed in the Xenotest device. The following differences emerge when assessing the lightfastness properties:

All not post-treated with the phosphine oxides or amine oxides or produced without these substances Colorings or the corresponding white materials treated without dye show extremely strong signs of yellowing, whereas with all post-treated or manufactured with the auxiliaries Samples hardly any yellowing due to incompletely removed residues of carrier preparations is visible.

Example 2

The following carrier settings are first made:

1) 43% o-phenylphenol,

43% decyl dimethyl phosphine oxide,
14% of a mixture

65% dodecylbenzenesulfonate,

20% butanol,

10% Sinarol-2-sulfamidoacetic acid tri-

ethanolamine 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 practical dyeing conditions - however, without the use of a dye - will now fabric pattern of polyester fibers in a liquor ratio of 1: 25 while l ¹ / »hours and treated at 98 to 100 ⁰ C with aqueous liquors with acetic acid to pH 5.5 are set and, in accordance with the corresponding samples, contain the following amounts of carriers - each based on the content of o-phenylphenol:

(a) 1.8 g / l of 1) at the beginning of this example

carrier preparation described,

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

carrier preparation described,

(c) 1.8 g / l of a commercially available carrier based on

o-phenylphenol.

After the "dyeings" have been completed, they are reductively cleaned in the usual way, rinsed, on the Air dried, and - as in Example 1 - in the Xenotest Gsrät, exposed according to the usual type of light fastness test.

This shows that with the commercially available (carrier treated material (c) a very strong yellowing, while the other two samples (a) and (b) this Show appearance only to a very small extent. When assessing the strength of this yellowing with the "gray scale" to assess the bleeding (according to ISO Recommendation R105, accordingly DIN 54002 and SNV 95806) are for the sample treated with the commercially available carrier (c) the Stage 2, for the other two samples (a) and (b ' levels 4–5 on the gray scale! comparable.

SO? 640/1

Claims (1)

with the addition of a carrier. The functional patent claim: tion of the Caraets is to be sought mainly in srinenegali- v aerendeh properties; for dyeing ν u * «.t under HT conditions also counts for poly- 1. Process for the production of real, w ^ nssmnss by usual dyeing at 105 5 g ^ ijfj ^ Sndertem carrier additive that cannot be influenced by dyeing accelerators. Dyeings on synthetic fiber material from up to 106 ^C J £% ^ ^ _16n »thermosol preferably linear polyester fibers, with insoluble c) ^^^ Jl ^ r? ämpf process, whereby Dyes, thus β? * «» »« »« ⁵ ** ¹ ^ leVStsaWauf mechanical, uniform that the dyeings are applied to the textile materials using the pull-out method in the presence of (^ substances as well as of ₁₀ * _d S _n ^ g of the dyes by a heat 2S £ S3 ^ JlääSS £ iiZ: SÄS ** —- «« - <* - * -