DE2056009C - Process for uniform and streak-free dyeing of synthetic polyamide fiber material - Google Patents

Description

R-CO-NH- / j>

R '

(D

SO ₃ M *

in the

R is an aliphatic hydrocarbon radical with

10 to 19 carbon atoms, R 'is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom and ^2S

M * means a monovalent cation

out of it; at temperatures from 40 to 100 ⁰ C, the solution is added at least one anionic dye and the coloring at temperatures zwisehen 95 and 140 ^c C completes.

2. The method according to claim 1, characterized in that a liquor is used as anion-active auxiliary contains a compound of formula II

For example, the simultaneous use of condensation products of naphthalene-2-sulfonic acid with formaldehyde and a weakly cationic auxiliary is recommended. Is also known the use of dibutylnaphthalenesulfonic acid mixed with certain cationic polyglycol ethers.

However, the streak-compensating effect of the proposed auxiliary systems often turns out to be as insufficient, which is why the results obtained with this method are unsatisfactory.

It has now been found that fiber material made of synthetic polyamide can be made uniform and streak-free can dye if the fiber material is at a pH value of 2 to 7 and at temperatures Treated from 30 to 100 ° C with a pretreatment liquor which is an anionic auxiliary of the formula I contains:

R -CO-NH

R '

SOf

in the

R is an aliphatic hydrocarbon radical with 10 to 19 carbon atoms,

R 'is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or represents a halogen atom and a monovalent cation.

(Π,

35

40

in the

R is an aliphatic hydrocarbon radical with

17 carbon atoms and M * means a monovalent cation.

3. The method according to claim 1, characterized in that there is a solution of at least one non-metallized acidic wool dye with a sulfonic acid group added as an anionic dye.

55

The present invention relates to a method 1 uniform and streak-free dyeing of synthetic polyamide material, in particular: synthetic polyamide with different dye affinity, as well as the fiber material dyed according to this method,
• he streak-free and even dyeing of: r material made of synthetic polyamide provides for

In many cases Därber is a difficult-to-resolve pronoun represents. To overcome these difficulties

various suggestions have already been made. ·

then the solution of at least one anionic dye is added at temperatures of 40 to ^100.degree. C. and the dyeing is completed at temperatures between 95 and 140.degree.

In compounds of the general formula I mean; R as an aliphatic hydrocarbon radical with 10 to 19 carbon atoms, a straight-chain alkyl or alkenyl group, such as dec-9-enyl, undecyl. Tndecyl, Pentadecyl, pentadec-8-enyl, heptadecyc heptadec-8-enyl or nonadecyl group. Preferably R represents a heptadecyl or, in particular, a heptadec-8-enyl group.

R 'denotes an alkyl or an alkoxy group with 1 to 4 carbon atoms, it is, for example, a methyl, ethyl, isopropyl or n-butyl group or around a methoxy, ethoxy, isopropoxy or n-butoxy group; means R 'a Halogen atom, it is, for example, chlorine or bromine. The group corresponding to R 'can in 0-, m- or p-position to the alkane or alkenamido radical stand. However, R 'is preferably hydrogen.

M ⁹ in the meaning of a monovalent cation represents, for example, an alkali metal cation or an alkylammonium or hydroxyalkylammonium cation with 2 to 4 carbon atoms, such as ethylammonium, n-butylammonium, / i-hydroxyethylammonium, di '/ f-hydroxyethylammonium, tri - / i-hydroxyethylammonium -. / f-hydroxypropylammonium or j-hydroxypropylammonium cation. Advantageously, however, M® denotes a sodium cation and, in particular, the ammonium ion.

The sulfonic acid group can be in the o-, m- or p-position to the alkane or alkenamido radical. The sulfonic acid group in the m-position is preferred.

Examples of those which can be used according to the invention are anion-active compounds of formula 1

l-Undec-lO-enamido-benzolO-sodium sulfonate
1 -dodecanamido-benzene-3-sodium sulfonate '

l-hexadecanamido ^ -methyl-benzolO-sodium sulfonate,

l-Octadecanamido-benzoM-ammonium sulfonate

l-octadecanamido-l-propoxy-benzene-S-potassium- ' sulfonate.

l-Octadecanamido- ^ butyl-benzene-S-sodium sulfonate,

l-Octadecanamido ^ -ethoxy-benzene-2-ammonium sulfonate.

1-Octadec-Q-enamido-benzene ^ - or
-4-sodium sulfonate.

1-Octadec-9-enamido-4-methoxy-benzene-2-sodium sulfonate.

1-Octadec-9-enamido-4-methyl-benzene-3-sodium sulfonate.

¹ Octadec ^ -inamido ^ -chlor- or ^ rmezolSnatrium ^ uÜonat.

l-Octadec-Q-enamido-ben / ol- ^ ithvlammon'umsulfonat.

ii: e.-Hydroxyäthylammoniuni-.
L) i -,; - hydroxyäthylammonium- and
! π -, .- hydroxyäthylarnmoniurh.Nalze der

l-Octadec-Q-enamido-benzene ^ -sulfuii acid.
! -Octadec-Q-enamido-l-butoxN-benzene-

3 -; - hydroxypropylammon: um> u! K.nat or

i-Eicosanami'lo-J-methoxy-bcn / ol-J-sodium sulfonate.

The anion-active HiIFsmitiol is advantageously used Compounds of the formula Π

R — CO — NH- '-

(II)

SO ₃ M

40

in the

R is an aliphatic hydrocarbon radical with

17 carbon atoms and
M means a monovalent cation. ^4S

in particular the sodium or ammonium salts of l-octadecanamido-benzene-B-sulfonic acid or the l-Octadec-Q-enamido-benzene-ß-sulfonic acid, especially but l-octadec-Q-enamido-benzoW-ammonium-sulonate.

The preparation of the anion-active compounds of the general formula I can be carried out according to known methods Methods take place, for example by condensation of the corresponding fatty acid halides with the aminobenzenesulfonic acids in the presence of acid-binding agents such as sodium hydroxide, ammonium hydroxide. Sodium carbonate, potassium hydrogen carbonate. Sodium acetate, ethanoiamine, diethanolamine or Triethanolamine.

Anionic dyes suitable for the process according to the invention can be very diverse Belong to dye classes. For example, it is azo, anthraquinones, quinophthalone, Phthalocyanine, tripbenyl methane, nitro or form & 5 azane dyes, which may also be complex-bound Metals such as copper, nickel. Chromium or cobalt. Come as azo dyes primarily monoazo dyes in question, e.g. B. such of the phenylazobenzene type. Phenylazonaphthalene, phenylazohydroxy or aminopyrazole, phenylazoacyloacetylarylamide or those of the analogous naphthylazo series. being the aromatic nuclei suitable can be substituted. Dis- and polyazo dyes are also suitable. Are the azo or formazan dyes metallized, so primarily by chromium or cobalt, with per metal atom 1 or 2 molecules of dye are involved in the complex. The anionic character can through Metal complex formation alone and / or through acidic salt-forming substituents, such as carboxylic acid groups, acidic sulfuric acid and phosphoric acid ester groups, 1 phosphoric acid groups or sulfonic acid groups. conditional being. Non-metallized acidic wool dyes with a sulfonic acid group are preferred.

The pH of the pretreatment liquor is expediently adjusted by adding an acid such as acetic acid, Formic acid or sulfuric acid, or a suitable pH-regulating salt, such as ammonium sulfate, brought to the desired value. The pretreatment of the fiber material at 30. preferably 40 to 100 C in the containing the defined auxiliaries The liquor preferably lasts 5 to 45 minutes. After the pretreatment one can check the acidity the liquor by adding an acid-binding agent, like ammonium hydroxide. Disodium or dipotassium hydrogen phosphate. Sodium or potassium acetate, as well reduce of hexamethylenetetramine.

An advantageous embodiment of the invention The method consists in performing the pretreatment at boiling temperature, then the pre-dissolved dye is added and the dyeing is completed at the same temperature. After Dyeing the material to be dyed is expediently rinsed in the usual way, if necessary to improve the After-treating wet fastness properties and drying.

In general, the anion-active auxiliaries are used in amounts of 0.2 to 5 percent by weight, based on the fiber material to be treated. preferably in amounts of 1 to 3 percent by weight.

It has proven to be particularly advantageous to use the anion-active auxiliaries according to the invention use in the form of storage-stable solutions. Suitable solvents are, for example, in addition to Water Mixtures of water and monohydric or dihydric lower aliphatic alcohols, such as Ethanol, ^ ropanol. Isopropanol or ethylene glycol, or ethers of lower dihydric alcohols, such as Ethylcnglykolmonomethyläthcr or ethylene glycol monoethyl ether. “Lower” alcohols are understood as meaning those with 1 to 4 carbon atoms. For the The corresponding ammonium sulfonates in particular have been used to produce such storage-stable auxiliary solutions of the compounds of general formula I have been found to be favorable. A particularly preferred one Preparation contains 10 to 60 percent by weight of 1-octadec-Q-enamido-benzoM-ammonium sulfonate in a mixture of isopropanol and water in a volume ratio of approximately 1: 4 to 4: 1. before all in a ratio of approximately 1: 4 to 1: 1.

The pretreatment or dye liquor can also contain other auxiliaries customary in dyeing, for example Electrolytes. Urea. Thiourea. Thiodialhylene glycol or hydrophilic compounds with limited water solubility, such as butyl or benzyl alcohol, contain.

As a fiber material made of synthetic polyamide, which is dyed according to the method according to the invention can come z. B. Condensation products from hexamethylenediamine and adipic acid (polyamide 6.6) or sebacic acid (polyamide 6.10) or mixed condensation products. z. B. hexamethylenediamine. Adipic acid and f-caprolactam (polymide 6.6 6). furthermore the Polymerization products from f-caprolactam. or from <«- arr.iiioundecanoic acid (polyamide 11) into consideration. These fibers can be used in any processing stage, e.g. B. in the form of threads. Ga. 3. Knitted and woven fabrics.

The method according to the invention succeeds. to dye synthetic polyamide fiber material streak-free and evenly. So it is surprisingly possible with a single anion-active auxiliary component to a balance of material-related affinity differences and at the same time to one Compensation for dye-related levelness get. Above all, it is unexpected that the migratory capacity, which is advantageous for the uniform loss of goods of the dyes in many cases by the addition of the amonakiiven substances which can be used according to the invention Aid is significantly increased.

In the examples below are the temperatures given in degrees Celsius.

example 1

0.2 g of ammonium sulfate and 0.15 g of a compound are added to 400 ml of water at about 40 ° formula

C ₁₇ H ₃₃ CO-NH

SOi

Well ^s

This liquor is used to treat 10 g of knitted fabric made of textured polyamide 6 yarn for 10 minutes of Ki 40. Then add a solution of 0.05 g of the dye of the ^c ormel to the liquor

SO ₁ Na

CH ₃

in 10 ml of water.

The temperature of the dyebath inside is increased with constant agitation of the textile material from 45 minutes to the boiling point and stains with gentle boiling for a further 60 minutes. On that the dyed material is rinsed with warm and cold water and dried.

In this way, a streak-free and uniform purple coloration is obtained.

The compound used as an auxiliary anionic active agent in this example becomes, for example, as follows receive:

52 g of metanilic acid are dispersed in 250 ml of water and by adding 27.3 ml of 30% sodium hydroxide solution brought into solution. The solution is then diluted with 300 ml of methyl ethyl ketone.

90 g of acid chloride and at the same time are then added dropwise to this solution at 0 ° to 5 ° within about 2 hours 27.3 ml of 30% sodium hydroxide solution, the pH of the reaction mixture being between 6 and 7 is held. Then 50 g of sodium chloride are added to the reaction mixture, whereupon a phase separation occurs. The organic plan, which d; <desired Revealed product in the dissolved state, is separated and in vacuo at 60 to 70 times Evaporated to dryness. 140 g of a white powdery crude product are obtained, which in his Composition essentially of the formula

C ₁₇ Hv ₁ CO-

SO ₃ Na
is equivalent to.

If in the previous example the 0.15 g of the anionic auxiliary used is replaced by the the same amount of one of the sulfonic acid salts listed in Table I below and the rest of the procedure As described in Example 1, similarly good colorations are obtained on the fiber material mentioned.

Table I. example Sulfonic acid salt Well © Na® 2 r
C ₁₇ H ₃₃ CONH - \ ~ V ~ SO ₃ ⁰
L. 3 C ₁₇ H ₃₃ CONH ~ \ ^ / so,-

continuation

example

Sulphanic acid sulphate

C ₁₇ H ₃₅ CONH

SO ₃ ⁶¹ Na®

C ₁₁ H ₂₃ CONH Na®

C ₁₅ H ₃₁ CONH - ^ y-CH ₃ SO ₃ ^e

C ₁₇ H ₃₃ CONH - ^ ~ ^ OCH ₃ Na®

SO ₃ ^e Na®

C ₁₇ H ₃₃ CONH - <> -CH

CH ₃ O

so ₃ ^e Na®

C ₁₉ H ₃₉ CONH

S0 ₃ ^e Na®

C ₁₇ H ₃₅ CONH

C ₁₁ H ₃₅ CONH (~ \ - S0 ₃ ^e NH ₄ ⁶

C ₁₇ H

₃₃ CONH - ^^ - SO ₃

C ₁₇ H ₃₃ CONH - \ ~ S

C ₁₇ H ₃₃ CONH H ₃ N ^

C ₂ H ₅

H ₃ N® — CH ₂ CH ₂ OH

H ₂ N * (CH ₂ CH ₂ OH) j

Io

continuation HN- (CH ₂ CH ₂ OHk example Sulfonic acid salt Na® If 16 C ₁₇ H ₃₃ CONH - \ ~ y
SO ₃ ^e - -
C ₁₇ H ₃₃ CONH - <^ ~ ^ CI S0 ₃ ö

example

0.2 g of ammonium sulfate and 0.5 ml of a 35% solution of the compound are added to 400 ml of softened water the formula

C ₁₇ H ₃₃ CO -NH

SO ₃ ⁹

in a mixture of isopropano) and water in a ratio of about 4: 7.

In this liquor, 10 g of knitted fabric made of textured polyamide 6,6 yarn for 15 minutes at 45 " pretreated. A solution of 0.05 g of the dye of the formula is then added to the liquor

CH

CH ₃

SO ₂ O

in 10 ml of water. The temperature of the dyebath is increased with constant movement of the material to be dyed within 45 minutes to boiling point and stains with gentle boiling during further periods 60 minutes. The dyed material is then rinsed with warm and cold water and dried

In this way, a uniform and streak-free red coloration is obtained.

The solution of the compound of the formula used as an auxiliary in this example

C ₁₇ H "CO—

SO ₃ ⁶

NH ₄ *

55

60

SO ₃ Na

aqueous 24% ammonium hydroxide solution was added dropwise so that the pH of the reaction mixture between 4,5 and 5 remains.

In this way, 258 g of a pale red-brown colored storage-stable solution of the compound are obtained the formula above.

If in this example 17 the dye used is replaced by the same amount as in example 1 The dye used and the rest of the procedure as described in Example 17, an identical one is obtained moderate and streak-free purple color.

Example 18

To 400 ml of softened water at 40 °, add 02 ml of 40% acetic acid and 0.1 g of the compound of the formula

in isopropanol-water in a ratio of about 4: 7 is obtained, for example, as follows:

35 g metanilic acid are suspended in 83 ml water and 66 ml of isopropanol and brought by the addition of 16 ml of aqueous 24% strength ammonium hydroxide in solution Then, to this solution at 0 to 5 ° the same time 60 g ülsäurechlorid UUD 17.5 ml Q ₇ H ₃₃ CC-NH

SO ₃ *

H ₃ N®-CH ₂ CH ₂ Ot

In this liquor 10 g of knitted fabric made of texturiei tem polyamide 6.6 yarn are for 15 minutes at 4C

rbehandell. A solution η 0.055 g of the dye of the formula is then added to the liquor

N = N

H ₂ N

CH,

SO, well

038 g of the dye of the formula

NH ₂

SO ₃ Na

ind 0.05 g of the dye of the formula

O NH

SO ₃ Na

NH-COCH ₃

CH ₃ CH ₂ NH-CO-

O NH-

CH ₃

60 minutes at boiling temperature. The colored material is then rinsed with warm and cold water and dried. One receives if adhered to under these conditions, with extensive exhaustion of the dyebath, a balanced, streak-free blue Coloring.

If one changes the dyeing conditions in this example 19, by instead of 60 minutes at boiling temperature only for 45 minutes, but at

ίο dyes 105 ° in a closed dyeing system under pressure, you also get a streak-free and balanced blue dyeing.

In this example 19, the 10 g tricot made of polyamide 6.6 textured yarn is replaced by 10 g of a knitted fabric made of non-textured polyamide 6.6 yarn and carries out the coloring in a closed system a temperature of 135 °, so the dyeing time can be reduced to 30 minutes. A streak-free and level blue coloration is obtained.

20th

Example 20

1.5 ml of the 35% solution of the auxiliary i < described in Example 17 are added to 200 ml of water at 70 °; using the formula

C ₁₇ H ₃₃ CO-

NH ₄ ®

and 0.2 ml of 85% formic acid. 10 g of a knitted fabric made of polyamide 6.6 textured yarn are now in the prepared liquor pretreated for 15 minutes at 70 °. Then the liquor is a solution of 0.04 g of the dye of the formula

in 20 ml of water. The dye liquor is then brought to boiling temperature within about 45 minutes and then stains for a further 60 minutes with gentle boiling. The colored material is then rinsed with hot and cold water and dried.

In this way, a very uniform and streak-free gray coloration is obtained.

Example 19

About 400 ml of water at about 40 ° are added 0.2 g of ammonium sulfate and 0.15 g of the auxiliary described in Example 1. 10 g of tricot made of polyamide 6,6 textured yarn are brought into this liquor. The temperature of the liquor is now increased rapidly to the boiling point, constantly moving the textile material, and the mixture is boiled for 30 minutes. A solution of 0.1 g of the dye of the formula O NH _{2 is then added to the liquor}

SO ₃ Na

, e

Löm! Water and then colors are added while in 5 ml of water and the liquor is heated to boiling within about 20 minutes. The material to be dyed is then dyed for one hour at boiling temperature, with constant agitation, and the dyed material is then rinsed and dried as usual

The resulting brown coloration is much quieter than one without the addition of the "ben listed" Coloring produced by means of auxiliary means.

example

14th

Muffs made of polyamide-6 textured yarn are placed in a Dffene dyeing device (packing apparatus). Is separated : ine about 40 ° warm liquor prepared (liquor ratio

C ₁₇ H ₃₃ CO-NH

and contains 2% ammonium sulfate.

This prepared liquor is pumped into the dyeing ice about 1:15), which, based on the weight of the Textile material, 5% of the 35% solution of the auxiliary of the formula described in Example 17

SOf NH /

The addition of dilute ammonium hydroxide solution increases the pH of the bath to 6.0.

contraption. The temperature of the 15 is then increased. After the liquor has been well mixed, it is set.

The liquor quickly rises to 95 ° and the dyed material is treated at this temperature for 30 minutes. Through based on the weight of the material to be colored. 0.6% dye of the formula

NaO ₁ S

0.3% dye of the formula

NH-

-N = N

NO ₂

Ο — SO,

CH,

and 0.35% dye of the formula

O NH ₂

¹¹ 'S 0, Na

CH ₃ CH ₂ NHCO

CH ₂ CH ₂ OH

CH ₂ CH ₂ OH

pre-dissolved in ten times the amount of water, and stains for a further 60 minutes at boiling temperature. Then will the dark brown colored goods are rinsed with warm and cold water and dried.

A knitted fabric made from the yarn dyed in this way is very uniform in color and free of Stripes.

If the aid used in this example is replaced by an appropriate mix of one of the ir the auxiliaries specified in Examples 1 to 16 and the rest of the procedure is as described in Example 21 so you get a similarly good product failure.

Claims (1)

Patent claims: 1. Process for uniform and streak-free dyeing of synthetic fiber material Polyamide, characterized that the fiber material at a pH of 2 to 7 and at temperatures of 30 to 100 ° C treated with a pre-treatment liquor, which is an anionic auxiliary of the Formula I contains