DE2146761B2 - Process for the production of lightfast dyeings and prints on synthetic fibers - Google Patents

Description

R-P, '

R-N

YR ₂

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 sulfonamide group denote interrupted alkyl or alkenyl radicals with 1 to 20 carbon atoms, the radicals XR, and Y —R ₂ or R and R _{8 being} components of a heterocyclic five or five formed together with the central phosphorus or nitrogen atom Can be 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 such auxiliaries of the formulas (1) and / or (2) produced therewith aftertreated and / or after the dyeing of this auxiliary in the aqueous, optionally acidic post-cleaning baths n or during the subsequent reductive cleaning of the dyed goods.

2. The method according to claim 1, characterized in that the organophosphorus compound and / or the amine oxide is used in the carrier preparation.

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

a) dyeing in an aqueous medium using the pull-out method at cooking temperature with the addition of a carrier, the aid being a fiber »opener« works. This results in a considerable increase in the color yield.

b) Dyeing by the exhaust method under HT conditions at 120 to 140 ⁰ C, if appropriate with addition of a carrier. The function of the carrier is mainly to be found in its equalizing properties; for dyeing under HT conditions further comprises conventional for polyester-wool blends dyeing at 105 counts to 106 ⁰ C under reduced Carrier additive.

c) Dyeing according to the so-called "Thermoso! - Process" or a steaming method, whereby the work process mechanical, even application of the dyes to the textile materials and fixing the dyes by a heat treatment (dry heat and / or steam).

d) dyeing from organic solvents according to a,. continuous or discontinuous operation, where uniform solvents, solvent mixtures (also azeotropic) or solvents / Water emulsions can be used in which the dyes are in solution or in in dispersed form.

It is in connection with the variants indicated above for the production of polyester dyeings known to the person skilled in the art that in many cases when dyeing with the addition of a carrier a deterioration in the lightfastness of the dyeings occurs if carrier residues remain in the fiber, In such cases, however, the different types of carrier differ quite a bit

_{3 <J} behave. The carrier systems η mainly used in practice today are based on the following chemical compounds as effective carrier components:

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, for example, methyl benzoate, methyl salicylate, mono-, di- and trichlorobenzenes or toluenes, etc., do not affect the lightfastness of dyeings or allow them to pass through simple treatments, such as drying in the air or at temperatures that are usual in practice Drying temperatures correspond to, remove again from the fiber. Are disadvantageous for these types of career compared to groups 3) and 4) their strong water vapor capacity (carrier spots), which in the In most cases, there is a stronger odor nuisance and that in the case of chlorinated, aromatic hydrocarbons present very strong toxicity.

The carriers summarized in groups 3) and 4) are mainly based on diphenyl, 2-Hydroxy-diphenyl and methylnaphthalenes built up. With regard to the influence on light fastness Of these three carrier substances, diphenyl behaves best by far. By a slight Heat treatment, for example at the drying temperatures customary in practice, can be carried out eliminate the residues of diphenyl remaining in the fiber during dyeing to such an extent that yellowing occurs and thus deterioration in the light fastness of dyeings no longer occurs. Quite The results are different for the two last-mentioned compounds: 2-hydroxydiphenyl and in particular In practice, methylnaphthalenes can only be removed from the fiber by special heat treatments

that have absolutely nothing in common with the term drying. In the case of methylnaphthalenes, which have the most unfavorable result on this point, for this purpose a minimum temperature of 140 ⁰ C is necessary, for example, in which the dry product must be treated for at least 3 minutes to the Carrier residues to volatilize to such an extent that deterioration of the The lightfastness of the dyed goods is no longer recognizable. For the practitioner, this means that carriers based on the last-mentioned compounds, which, incidentally, are very well established and widespread in practice, have their limits and can no longer be used where no such special post-heat treatment can be carried out, if so For example, the machine requirements are not met (e.g. when drying muffs) or the fiber properties may be impaired (e.g. in the case of textured fibers). In addition, it should not be overlooked that the previously mentioned "more severe drying conditions" mean a not entirely insignificant energy deficit.

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, with insoluble dyes leave if you do the dyeings after 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
RP _x

YR ₂

R ₂

(1)

(2)

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 sulfonamide group are interrupted alkyl or alkenyl radicals with 1 to 20 carbon atoms, the radicals XR ₁ and Y - R ₂ or R ₁ and R _{2 being} constituents of a heterocyclic five or five formed together with the central phosphorus or nitrogen atom Seciisrings, 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 are a direct bond and / or an oxygen atom, or without the use of auxiliaries Formulas (1) and / or (2) dyeings produced therewith aftertreated and / or added after dyeing this auxiliary in the subsequent reductive cleaning of the dyed goods t.

According to the present invention, it is now possible without deteriorating the lightfastness to have to fear carrier substances of the latter types when dyeing synthetic fibers to be used, whereby the special post-treatment is not necessary when in the dye bath, in the post-treatment bath or products of the general formulas (1) or (2) are also used in the carrier preparation will.

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

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-palmitic acid amidopropyl dimethyl

phosphine oxide,

Hexyl-methyl-butyl-phosphine oxide,
Hexyl dimethyl phosphine oxide,
Propyl methyl phosphinic acid isobutyl ester,
Dudecyl-methyl-phosphinic acid-ethyl ester,
2-chloroethyl dodecyl methyl phosphinate, isobutyl decyl methyl phosphinate,
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 - Dodecy 1-piperidine- N-oxide,
Tetradecy 1-di methy 1-ami oxide,
Coconut fat dimethyl amine oxide,
Oleoyl-amidomethyl-dimethyl-amine oxide or
Hexadecyl bis (/ 9-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 in connection with the claimed process It is irrelevant whether these are used in an aftertreatment bath or in the dye bath directly or indirectly, d. H. with the addition of a special carrier preparation.

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

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 approximately 10 to 20 minutes at temperatures between room temperature and boiling temperature, preferably carried out at 50 to 90 ⁰ C. This post-treatment process can also be combined at the same time with the reductive post-cleaning that is customary for polyester dyeings, i.e. the indicated auxiliaries are either additionally added to the reductive post-cleaning bath containing alkali, reducing agent and usually a detergent, or possibly also in the reductive post-cleaning liquor instead of the usual detergent be used.
Another option for adding the organophosphorus compounds or amine oxides mentioned is direct addition to the dyebath, whereby the products can be added as soon as the dyeing process has started, but preferably only when it is added to the dyebath

35

of the last third to quarter of the total dyeing time Example 1 j be admitted.

Yet another variation of the polyester staple fiber yarn according to the invention is in the liquor ratio

Method is said products of 1: 25 for 90 minutes and at 98 to 100 ⁰ C in j formulas (1) or (2) a dye bath initially treated in the Carrierzuberei- 5, which - based on the I

tion, whereby when adding .les with the weight of the dry goods - 0.1% of the dye

Auxiliaries produced carriers at the same time an in the formula j The products are added directly to the dye bath. j

The commercially available O NH _{2 introduced in practice}
In addition to minor additions (such as io

for example stabilizers for the shelf life of y \ Z \ Z \ q (CH ₂ ) OH

Preparation, tools for improving the emulsions. ι
alloying, re-emulsification, emulsion resistance, etc.)
the following main components:

Carrier-effective substance (possibly also a 15
several carrier active substances),
Emulsifier (mostly mixtures of different

Emulsifiers) and optionally a dissolving aid and 4 g / l of a commercially available carrier on methyl agent. In the case of using room-temperature naphthalene-based (with about 60% effective carrier temperature, liquid carrier-active compounds becomes 20 substance) and this is adjusted by means of acetic acid to the use of a pH value of 5.5 in most cases is.
Additional solvent auxiliaries are dispensed with, ie the carrier is also, under otherwise identical conditions, mainly containing the liquid carrier - a "blind" color without the above-mentioned active substance and emulsifiers. Made in such a dye on the same material.
Case can be obtained by simply mixing in the invention Products into the dye bath is enabled. Treated material looks different, is then divided into two samples, which are the same at room temperature, and a sample of these stain-resistant, carrier-active compounds is then used; In this case, the usual in polyester dyeing is subjected to an additional advantage when using the reductive post-cleaning, rinsing and organophosphorus compounds or amine-dried in the air, while the other two oxides occur. Usually samples are only rinsed and air-dried at room temperature, solid carrier-active substances in most cases. The 4 samples now available are then first dissolved in a solvent; after 35 again divided into several parts, and with the addition of emulsifiers then one liquid results from each series - in each case with a liquor ratio of 1:20 carrier setting. On the market, of course, as well as in aqueous liquor - the following also some carriers have been carried out in paste or dough form treatment processes:
meet, which consists of solid carrier-active substances, "_ ... ... . .. .. ,, _w . ,

have been prepared without a solvent. At 40 ^L 3 g / l decyl dimethyl phosphine oxide, 15 minutes

Practitioners enjoy these carrier preparations _, .. "'. ",,. ..,. .. "" ...

but not all that popular, since their hand- ² x 3 g / i coconut fat-d.methyl-aminox, (L 20 minutes

habung always associated with greater difficulties ^{Dei u}

The two samples that were not previously reductively cleaned

Government, certain minimum temperature of the dyebath 45 are also connected respectively for 20 minutes at 85 ⁰ C.

before adding the carrier, etc.). By using one of the aqueous liquors given below

of the products of the general formulas (1) and (2) composition post-treated:

it is now possible to use liquid carrier settings. "" _ ... ... .. ..

Basis of carrier active at room temperature ^a > 2 g / decyl-dimethyl-phosphine oxide,

seed compounds without the addition of a 50 5 m / l sodium hydroxide solution, 32.5%,

so that the solid carrier- ² 8 (sodium dithionite and.

active substance in about the same amount of the ^l ^ ^emes detergent based on an alkyl

mentioned auxiliaries, possibly by light Er- .., _ pnenolpolyglykolathers;

warm, dissolved and then with an emulsifier ^b > ³ _e g / decyl-dimethyl-phosphine oxide,

is mixed. By adding these Carrier-Einste- 55 * m / 1 sodium hydroxide solution, 32.5 ^ ig and

Lungs in the dye bath can also be achieved, as in ² »'sodium dithionite.

previously described case, an indirect addition of all post-treated samples are then made

products recommended according to the invention for dyeing - rinsed and air-dried,

bath. In addition to the post-treatment

The method according to the invention is suitable for the 60 operations for staining that do not involve any involvement

Production of dyeings on synthetic fibers - the auxiliary according to the invention were produced,

materials, such as linear polyester, are also colored separately according to the

Polyamide, polyacrylonitrile or cellulose triacetate methods explained at the beginning or manufactured

fibers that are also mixed with each other or in treatments of the material without dye

Mixture with natural fibers such as cellulose or 65 leads, in these cases 3 g / l decyl-dimethyl-

WoIIe, may be present. As colorants for these maphosphine oxide

materials come e.g. B. Dispersion, acid and water a) the dye bath from the start of the dyeing process,

insoluble metal complex dyes in question. b) the Färh ^ hp ^ ~ o "i- 1 *" ■ - ^j ■ - ■

vd
at
" ¹ O

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. When assessing the lightfastness properties, the following differences arise:

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

30th

The following carrier settings are first made:

1) 43% o-phenylphenol,

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

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, the adjusted with acetic acid to pH 5.5 and, in accordance with the corresponding samples, the following amounts of carriers - each based on the content of o-phenylphenol - contain:

(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, rinsed and cleaned in the usual way Air dried, and - as in Example 1 - in the Xenotest device, exposed according to the usual type of light fastness test.

The material (c) treated with the commercially available Carriei shows a very strong yellowing, while the other two samples (a) and (b) show this phenomenon only to a very small extent, When assessing the strength of this annoyance with the "gray scale" to assess the staining: (according to ISO Recommendation R105, accordingly DIN 54002 and SNV 95806) are for the sample treated with the commercially available carrier (c) di < Level 2, for the other two samples (a) and (b, levels 4–5 on the gray scale! comparable.

■ '.- η
nit
■ cn

$ 09508 * 3!

Claims (1)

Patent claims: 1. Process for the production of lightfast, not influenced by dye accelerators Dyeings on synthetic fiber material, preferably linear polyester fibers, with insoluble ones Dyestuffs, characterized in that the dyeings are made by the exhaustion method in the presence of carrier substances and organophosphorus compounds of the general Formula (1) and / or amine oxides of the general formula (2)