DE1619381A1 - Process for dyeing nylon in pink shades - Google Patents

Description

Patent attorney

Br.-Ing. Wilhelm Reichel Frankfuri / Main-1 ■. -_ ■

Parksiraßel3 1619381

4687/4688 Crompton & Knowles, Worcester, Massachusetts, U, S.A.

Method of dyeing.3JyIon in pink shades

The invention relates to a method of dyeing natural and synthetic polyamide fibers in washeehten _ff bluish-red or rpsa shades ",

In particular, the invention relates to ice Dyeing-natural or synthetic © » which the fibers at room temperature in 9ln neutral, watery bath Contains dye with the following structural formula?

fi NH ₂

(structure A) '

In it, the symbol R is hydrogen or an alkyl roast with 1 to 9 carbon atoms. The temperature of the bath is then raised to about 93 ⁰ Q (200 ⁰ F) and the fibers remain in contact with the dye bath for a sufficient period of time to draw dye onto the fibers. The pH of the bath is then lowered in order to make the bath slightly acidic, whereby the fibers and the acidified dye bath remain in contact until the bath is completely exhausted. The dye is then removed from the bath.

BADOHWINAl 109823/2087

As described in the patent application (US Serial Ho. 452 868) filed on the same day _{, the dyes with the structure A t} which are used according to the invention are obtained by sulfonating known 1-amino-2-pheno: xy-4-hydroxy -anthraquinones, which contain an unsubstituted phenoxy ring or a phenoxy ring equipped with 1 to 9 carbon atoms, so that the right conditions are created for the storage of a single sulfo group in the dye.

The non-sulfonated anthraquinone precursor compounds of the dyes with der.Struktur A are known to be suitable as disperse dyes for synthetic fibers. When used as disperse dyes, they lead to red shades of acetate, sria @@ tat "modaeryl, polyester and ITylon fibers, ₉ while they merely stain cotton, acrylic, silk and wool fibers without dyeing them.

The dyes with structure A are unique and unexpected properties when you look at them with theirs

compares non-sulfonated precursor compounds. There are neutral coloring acid dyes for natural and synthetic polyamide fibers such as silk, wool and uylon. You don't dye and have a good ability to preserve acetate, Triacetate, acrylic, modacrylic and polyester fibers.

The dyes with structure A provide the polyamide fibers with light, bluish-red shades of high lightfastness · Compared to their non-sulfonated anthraquinone precursors: far achieve, the dyes with structure A a greater washing

109? ° _{23/2087 tAD}

fastness for a given depth of shade and greater fastness to sublimation. Post -treatments with known fixing agents, e.g. tannin, tartar, so-called back tanning agents or synthetic tanning agents (syntans), etc., increase the washfastness of the dyeings produced with the dyes with structure A considerably, whereas such post-treatments are used for those drawn up as disperse dyes, non-sulfonated precursor compounds have little or no effect on the wash fastness

When using the method according to the invention are preferred such dyes with the structure A used «whose alkyl radicals R have five to nine carbon atoms, since these Dye nylon with high color utilization from a neutral solution, which reduces the risk of fiber degradation, which can consist of hot, strongly acidic dye baths during dyeing. If the alkyl radical has fewer than five carbon atoms contains, then the colorability is from a neutral solution less, while with ten or more carbon atoms in the alkyl radical, the colorability with neutral baths always stronger decreases "

The sulfonation of the anthraquinone precursor compounds is known in the art with acids of various concentrations Different long times and different temperatures are carried out to allow a sulfo group in the dye molecule built-in The exact position of the sulpho group in the phenoxy ring is not known. It can be the ortho or meta position, but it can also be a mixture of ortho and

Ium 3/2087 BAD ORIGINAL

Molecules substituted in the keta position act · In every JPaIl become anthraquinone precursor compound and oleum in such Amounts brought to a reaction that on average only one BuI-fo group is stored in the dye molecule »sulphonation is ended by a solubility test of a drop of the sulfonated reaction mass obtained in hot water. When the sulfonation is complete, there is no insoluble starting material observed.

When carrying out the process according to the invention, the fibers are left in the neutral position until dye has been absorbed onto the fibers. With most dyes of LJtruktür A (200 F ⁰⁾ (pH 6.5 to 7.5) proceed at temperatures of about 93 ⁰ C for thirty minutes already a substantial proportion of the dyestuff from the dyebath onto the fibers neutral · For complete When the dyebath is exhausted, the pH value of the bath must then be lowered to the slightly acidic area. When using a dye of the structure A with an alkyl group having five to nine carbon atoms, a complete exhaustion even at pH \, ^r Erten be obtained by 6, while occurs when using the remaining dyes of ütruktur A until complete exhaustion, when the pH value is lowered to about 3.5. In both cases, the fibers are held again about 30 Liinuten at elevated temperatures of about 93 ⁰ C (200 ⁰ F).

The following examples show the preparation of the dyes with structure A and their properties and usability.

U 'S d I -ic & "J ü S

144 g Oetylphenol, 11.8 g of calcined potassium carbonate and 20.4 g i ~ amino-2-bromo-4-hydroxy-anthraquinone are heated with stirring to 15O ⁰ C and 5 hours held at this temperature * After cooling, methanol was added and the resulting slurry (500 ml) is filtered. The residue is washed Mife methanol and then water and then dried ISLT · are obtained: 8 _r 8 g of i-An) inD-2 ~ octylphenoxy "-4-hydroxy-aBthraohinoii. 10 g thereof are sulfonated by being added is 30 minutes under RUtiren to I ^ 25 ml #igen oleum, while span the temperature below holds SO by means of a Kühlbadea ⁰ C. After stirring for four hours at room temperature, the sulfonated mass is soaked in ice and water and then filtered. The residue is slurried in water with sodium hydroxide solution

-5-

BATH

109823/2087

neutralized, filtered and dried. A dye is obtained in structure A ₁ . in what area

nu VT

- c — c —c - / I /

CH ^. H CH, Has.

140 g of p-amylphenol terfciäres, 11.8 g of potassium carbonate and calciniertea 25 »g of 4-amino - ^ - bromo - ^ - hydroxy-anthraquinone are heated under Rührur ;, on '50 ⁰ C and held for 5 hours at this temperature. After cooling, methanol is added, the resulting pulp is filtered and the residue is washed out with methanol and then with water. After drying, roan receives 25.8 g of i-Amino-i-amylphenoxy-4-hydroxy-anthraquinone 10 g of which are sulfonated with 150 g of 25 tiger oleum for 3 hours at 12 ° C. 5Yes - after soaking in ice and water (volume 500 ml at 12 ⁰ C) is filtered. The residue is mixed with water, made alkaline with sodium hydroxide solution to a pH of 9 ₉ 5, heated to a boil and then filtered. 100 g of ethanol are added to the filtrate. The precipitate is filtered and dried. A dye of the structure Aj in which R & ij form is obtained

/ - 3
has' ¹ T

-6 - _m

109823/2087

Beie |> iel _w 5

36.4 i-Araino-2 ~ bromo ~ 4-hydi? ®3 £ y-aattiraoM5a © n ₉ 14® g 85 I & gee phenol and 20.5 g potassium carbonate are suffered at ΐ20 ° 3 and the water is distilled off at this temperature held. After 18 hours at 120 ⁰ O, the reaction product is cooled and diluted with water (800 ml). It is then filtered and the residue is washed out with water until the filtrate remains colorless. After drying, the residue of i-amino-2-phenoxy-4-hydroxy-antteaehimony weighs 32 "8 g" 10 g of which are sulfonated "by being with stirring to 150 g of 25 cowardly Oleusj _s are aan while the temperature using a cooling bath at 21 ° · 24 ⁰ O established. After stirring at 24-28 ⁰ C is saturated with ice water until "Bi e at 28 ° C obtained 400 sil be the product filtered. The residue is dissolved in water and sodium hydroxide solution is brought to a pH of 11.0. It is then ^{heated to 60 °} C. and filtered. Eu 1000 © 1 of the piltrate are added to 100 g Sale, the pH is brought to 7-4 with hydrochloric acid, and the precipitate is filtered off and dried. "A compound of structure A is obtained with hydrogen for R"

EeispJLel_4

1 "? 0 g p-tertiary butyl phenol _f 11.8 g anhydrous potassium carbonate and -? 5 g i-Amirio-r-biomo-d-hyfcoxy-anth ^ aquinone are stirred to ΓίΟ ° * ~ * cnt2t and kept at this temperature for 6 hours. After cooling, 300 ml of methanol are sugeg @ * b @ n _s and the resulting oil is filtered, after washing out © it Me-

BATH ORIGINAL

ethanol and then with water, the residue is dried. 23.5 g of i-amino- £ ~ p-te; rtobutylphenQxy-4-hydroxy-anthraquinone are obtained. 10 g of this are sulfonated by adding them to 150 g of 25 # oleum for 10 minutes, the temperature being medium? a cooling bath at 17-19 ⁰ C is kept. After stirring the product for three hours at room temperature, it is soaked in ice and water. The resulting 400 ml are filtered. The Pi It he residue is dissolved in water containing 10 i »£ as containing neutralized to elutriated" with sodium hydroxide solution, filtered and dried. A connection with the structure A bit is obtained

CH ₃

CH ₃

for R.

110 g Nonylphenel ,, 11> 8 g of calcined potassium carbonate and 25M g i-amino-P-bromo ^ -hydroxy-anthraquinone be 5 hours at 150 ⁰ C for. After cooling, 160 ml of methanol and then 40 ml of Wasger are added. The slurry is filtered and the I ^ jLlterrückstand is tigern with 80 methanol and then with water au ^ overall wash * After drying, 26.8 g of 1-amino-2-phe ~ ^ hony Noxy-4-hydroxy- anthraquinone. 10 g of it are then sulfonated to the same level as in Example P , where έΐη

-8th-

8AO

109823/2 0 87

of structure A, in which R is an alkylreate with 9 carbon atoms and a branched chain.

BeiB |> iel_6.

0.5 g of the dye according to example 2 (sulf ^ niertea 1-fcaino-2 ~ p ~ amylphenoxy-4-hydroxy-anthraquinone-sodium al8) are dissolved in boiling »soft water, whereupon the volume de? The dye-off solution is brought to 500 ml with more soft water. 5 ml of this solution are then placed in four 400 nl staining beakers and made up to 250 ml with which water. The pH value of the Pärbelöaungen is 8.4 at 22 ⁰ O. A. multi-thread «5 g pieces made from strips of acetate, acrilan, (aoryliech), arnel (Triacetate), cotton, Crealan 61 (jcryliech), Daoron 54 (poly-

Dacron 66 (polyether) ester), Orion 42 (acrylic), silk _f V «rel A (modaoryliech), Vie Coae and wool are immersed in one of the four swirl solutions at room temperature, while a 5-g piece of blunt tricot made of nylon is inserted into each of the other three dye solutions. The temperature of the solutions is desin to 93 - 99 ⁰ C (200 - 210 °?) Increased »During the Firbefae thaw Ιψ. every (

Put a stirring tab in the staining beaker, ia hold the substance ia 3®M smoothly. Half an hour at 93 - 99 ⁰ C (200 - 210 ⁰ F). are added to one of the dye vessels with a lylon tricot, 5 tablespoons of a 10-part honey sodium phosphate solution, which gives the dye bath a pH of about 6. To another dyeing beaker with a nylon tricot, 5 ml of a TO> igen acetic acid solution are added, a dyeing bath with a pH of

~ ⁹ ~ ORIGINAL BATHROOM

109823/2087

3.5 results. After another half hour at 93 - (200 - 210 ⁰ F) become the single thread piece and the lylom piece removed, rinsed in Yaaaer and dried

The nylon, silk and woolen bands of the 'ehrfadigen pieces are colored red, while the polyester fibers are only slightly leaking lit. Lie nylon thicknesses are all colored with roughly the same ti ife. T) Ie baths to which mononatrium phosphate and acetic acid are added show a complete shade of color. In a neutral dye bath only a trace of color remains. If the dyeings are carried out in the same way with the dye obtained according to Example 1 (sulf eniertsa 1 -Amlno ^ -octyl-phenoxy - ^ - hydroxy-anthraquinone) then In the neutral dye bath, even less color remains after dyeing than when using the dye obtained in Example 2 (sulfonated i-alino-2-amylphenoxy-4-hydio :: y-anthraquinone). If, on the other hand, the dyeings are carried out with dyes derived from phenol (JJeisplel 3) or alkylphenols whose alkyl radicals contain less than 5 carbon atoms (Example 4), then the dye solution is still strongly colored after the neutral dyeing and contains almost the same or even greater color shade than the neutral color on the nylon jersey itself. This is determined by adding 5 ml of an esoiga acid solution to the remaining neutral bath from which the dyed nylon piece has been removed \ _s dipping a fresh piece of nylon pieces

BATH 10982372087

and the coloring until only exhaustion of the dye bath fortaetet · lach Wash and dry the deep “daa color tone then“ it compared to that of the neutral color. .

Bei3giel_7

0.2 g of the dye from Example 2 are mixed with 1200 ml of soft water, which is boiled to improve solubility. The dye solution is cooled to 71 ⁰ C (160 ⁰ P) · There are four immersed 5 g of matte Stüeke Iylon 66 jersey. 99 C ^D - while the pieces in the dye bath, stirred, temperature · dl to 93 (200 - 2 0 ⁰ P) increased and fir obtain an hour upright, unwound and then the pieces and dried. Pas nylon has been given a light, bluish red color.

Example_8

0.2 g of a non-sulfonated dye (i-amino-2-p-ter ';. Anylphenoxy-4-hydroxy-anthraquinone), which is used in the preparation of the dye according to Example 2, are dissolved in 20 oils of acetone. This solution is added to a solution of 2 g of lignin sulphonate in 1200 nl of soft water, which is in a dyeing vessel, and the acetone is removed by boiling. Four 5g pieces of nylon tricot are immersed. 99 ⁰ C - while the fabric is gerühtt in the dye bath, a temperature between 93 an hour long (200-210 ⁰ F) is maintained, whereupon the cooled pieces and dried. The nylon has acquired a matt, bluish-red color.

-11- ί

(BAD QRK3ÜNAI

109823/2087

Two of the following solutions are prepared: Solution As 0.2 g Cenekol (Althouse) in 300 oil-soft water. Solution Bs 0.5 g Erional N ₄ W. (öeigy) in 300 ml soft water. Solution C: 0.1 g tannin, 0.1 g acetic acid, 0.1 g vomit is one in 300 ml soft water.

A piece of fabric dyed according to Example 7 is immersed in one of these solutions, while a piece of fabric dyed according to Example 8 is dipped into the remaining solutions. The two rows of solution A, B, C in all of a 5-g pieces is immersed in colored nylon fabric are heated to 82 ⁰ C (180 ⁰ P) and held for about 20 minutes at this temperature. The fabrics are then unwound and dried. Together with the corresponding non-post-treated stitches v /., All pieces treated in solutions A, B and 0 are treated according to a US standard washing state (AATCC Standard Read Method 36-1961). All fabrics produced and reworked according to Example / have an improved washability compared to the untreated fabrics dyed according to Example 7. All fabrics which have not been "aftertreated" or which have been post-treated according to this example and which have been dyed according to Example 7 have a greater washfastness than all fabrics which have been dyed according to Example 8, even if one uses this Relnpiels treated. The warmth fastness of the fabrics dyed according to Example 8 is therefore low and cannot be improved even by one post-treatment according to this example.

-12-

109823/2087

BATH ORIGINAL

When dyeing fabrics composed of mixed fibers, e.g. polyester-polyamide mixtures, the use of Dyes with the structure A, in which R is an alkyl derivative with 5-9 carbon atoms, better control of the coloring by the dyer, because of the substantivity of the dye towards the polyamide and the reserve capacity of the polyester is enlarged.

In addition to the free acid, the compounds of the structure A _f which are used in the process according to the invention can be: & ueh their soluble salts. · 'V

BATH

10S823 / 2087

Claims (6)

Claims 1) method of dyeing natural and synthetic polyamide fibers, characterized in that the fibers into essentially neutral, aqueous, and Dye with the structural formula containing bath «where the symbol H is either Hydrogen or an alkyl reet. with t t> ie 9 carbon atoms means, and that the fibers should be removed from the remain in it until dye exercises on the fibers gangan is. 2) Method according to claim 1, characterized in that that the pH of the dye bath o between 6.5 and 7 »5 lies. 3) Method according to claim 1 or 2 _f characterized in da.5 a dye having Vasaerotoff or Alkylreet tn.it vjeniger than 5 hydrogen "Tomen IIIR the symbol H · used. Ird and DAJ dea by drawing a VRO" eentliehen ieile de ? Dye a; ujf the fibers of the pH value to complete exhaustion d.) 3 dye baths in the acidic area binain ßesenlct v.ird. 109823/2087 bad original 4-) procedure n eh one of the plurality © & βϊ · Aiuiptfldlte-1 Ms 3 # ä ^ aiure'i gekefin eiehce _t; In general, the dyebath during the carving phase. an increased temporality g®! rltea becomes *: "- ■". · 5) - 'Method according to claim 4, since ύ ua *; ch ' ^: ' g ® & e η a * · indicates that the faeerh are introduced into the dye bath at around zinc freezing temperature and that the! v; ird _e 6) The method of claim 1 wherein _t, confess »^ characterized öä3 di © dyed fibers Rait a Pii! Iermittel nächbehanöelt v- 75 The method according to claim 2, dadmroh gekfäa draws that the polyamide fibers with polyester fibers rerdea BATH 109823/208?