DE2124617B2 - METHOD FOR GENERATING MULTITONE EFFECTS ON FIBER MATERIAL MADE FROM POLYACRYLNITRILE OR POLYACRYLNITRILE COPOLYMERS - Google Patents

Description

R ₁ - (CO-NH- (CH ₂ ) J ^ ₁ -NX ₂

Air (1)

n-y;

N-Y,

At

-H

W,

CH ₃ SO ₄

contains, wherein R _{1 is} an alkyl radical with 8 to 18 carbon atoms, X ₁ and X _{2 are} each hydrogen, optionally substituted by hydroxyl, lower alkoxy or cyano, lower alkyl, cycloalkyl or a polyalkylene glycol radical, or X ₁ and X ₂ together with the nitrogen atom connecting them Piperidine or morpholine ring, X ₃ hydrogen, lower alkyl or aralkyl optionally substituted by hydroxyl or lower alkoxy, or X ₁ , X ₂ and X ₃ together with the nitrogen atom connecting them a pyridine ring optionally substituted by lower alkyl, one of the radicals R ₂ , V ₁ and V _{2 represent} an alkyl radical with 8 to 18 carbon atoms and the other hydrogen, optionally substituted by hydroxyl or alkyl or aralkyl, Z a saturated or unsaturated alkylene radical with 2 or 3 carbon atoms, Y ₁ , Y ₂ and Y ₃ each hydrogen, optionally through Hydroxyl or lower alkoxy substituted lower alkyl, cycloalkyl or aralkyl, Q sulfur or - NH-, r and s each 1 or 2, η 2 or 3, An the anion of an organic or inorganic acid, R ₃ an unsubstituted alkyl group with 8 to 18 carbon atoms and W] and W ₂ each denote lower alkyl which is optionally substituted by hydroxyl.

Good results are achieved above all with a cationic organic ammonium compound Formula 1 received.

The use of cationic organic ammonium compounds is particularly advantageous the formula

R ₁ -NX ₁
\

At

wherein R ₁ . X ₁ . X ₂ . X, and An have the meaning given.

Among the ammonium and The following 8 types of compounds have proven to be of particular interest for sulfonium compounds:

1. Compounds of the general formula

X ,,

by condensation of Cocosölfcttsüurechlorid with N.N-Dimcthylpropylenediamine and the salts of from these condensation products by reaction with dimethyl sulfate, glycol chlorohydrin. Epichlorohydrin or benzyl chloride available quaternary compounds mentioned.

3. Compounds of the general formula

At

in which R _{3 is} an unsubstituted alkyl group having 8 to 18, preferably 12 to 18 carbon atoms, X ₄ and X ₅ are each independently hydrogen, a lower alkyl radical optionally substituted by hydroxyl, lower alkoxy or cyano groups. a cycloalkyl radical. especially the cyclohexyl radical. or a polyglycol ether chain with 2 to 40, preferably 5 to 20 alkyleneoxy groups, especially ethylenoxy groups. and optionally individual propylenoxy or phenylethyienoxy groups or X ₄ and X ₅ together with the nitrogen atom connecting them a piperidine or morpholine, X ₆ water. a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups or an aralkyl radical. especially the benzyl radical, and An the anion of an organic or inorganic acid, such as the anion of the ant. Represents acetic, hydrochloric, hydrobromic, sulfuric, phosphoric or methylsulfuric acid.

As examples of suitable compounds of the formula b may be mentioned: by definition, salts of N-dodecyl-N-cyclohexylamine, N-dodecyl-N-benzylamine. N-cyano-ethyl-N-dodecylamine. N, N-bis (p'-hydroxyethyl) - N - dodecylamine, N N - bis - (/ * - hydroxyathyl) -N-octadecylamine. N-octadecynyl-piperidine; of condensation products of dodecyl, tetradecyl, octadecyl and octadecenylamine with 2 to 40 moles of alkylene oxide. especially ethylene oxide, such as the condensation products of octadecylamine with 20 moles of ethylene oxide or of octadecenylamine with 10 moles of propylene oxide. Of the polyethylene oxide addition products those with short ethylene oxide chains are preferred.

Examples of suitable quaternary compounds of the formula 6 are: N-dodecyl-NNN-trimethylammonium-methosulfal, N-dodecyl-RN-dimethyl-N-benzylammonium chloride, N-dodecyl-N, N-diethyl-N- β- hydroxyethyl-ammonium chloride, N - etradecyl-NN-dirnethyl-N-benzylammonium chloride, the reaction product of octadecylamine with 10 moles of ethylene oxide, quaternized with dimethyl sulfate, and the reaction product of dodecylamine with 7 moles of ethylene oxide, quaternized with epichlorohydrin. 2. Compounds of the general formula NR,

At

(8th)

20 in which R _{5 is} an unsubstituted or further substituted alkyl chain with 8 to 18, preferably 12 to 18 carbon _{atoms, optionally interrupted by oxygen atoms, and R 6 is} hydrogen, the methyl group or ethyl group, and An 'has the meaning given

Examples of suitable compounds of the formula 8 are: dodecylpyridinium chloride, octadecylpyridinium chloride, Dodecyl-3- or -4-methylpyridinium chloride and Octadecyloxymethylpyridiniumchlo-

rid.
4. Compounds of the general formula

3 ° (CH ₂ ) ,,

C-R,

At

(9)

in that of V ₄ . and R ₇ one is an unsubstituted alkyl group having 11 to 18 carbon atoms and the other is hydrogen or one optionally through

Lower alkyl radical substituted by hydroxyl groups, V _{3 is} hydrogen and - if V ₄ or R _{7 is} not hydrogen - also a lower alkyl radical optionally substituted by hydroxyl groups or an aralkyl radical, especially the benzyl radical,

means and η and An '"has the meaning given.

Examples of suitable compounds of the formula 9 are: 2-heptadecylimidazolinium acetate. 1 - β - hydroxyethyl - 2 - heptadecyl - tinidazolinium chloride, l - /? - hydroxyethyl-2-heptadecyl-3-methylimidazolinium methosulfate, 1 - undecyl - 2 - methylimidazolinium chloride and 2-heptadecenyl-tetrahydropyrimidinium chloride.

5. Compounds of the formula

R ₄ -CO-NH- (CH ₂ J _n -NX ₇

X ₈ y

To «(7)

55

in R ₄ an unsubstituted alkyl group with up to 17 carbon atoms, X- and X ₈ each represent an unsubstituted lower alkyl group and X ₆ , «and An» - have the meaning given.

Examples of suitable compounds of the formula 7 are salts according to the definition of compounds which V ₅
CH - N

CH-N

CR ₈

On ₁

in V ₆ an unsubstituted alkyl group with 12 to 18 carbon atoms, R ₈ hydrogen, an unsubstituted alkyl group with up to 18, preferably

A09 521/426

ίο

up to 4 carbon atoms or the unsubstituted phenyl radical, V ₅ an unsubstituted lower alkyl group or the benzyl radical and An; ^{1 represents} the anion of hydrochloric or hydrobromic acid or methylsulfuric acid.

Examples of compounds of the formula 10 are: 1-dodecyl-3-benzyl-imidazolium chloride and 1-hexadecyl ^ -isopropyl-S-methylimidazolium methosulfate.

6. Compounds of the general formula

8. Compounds of the formula

N-Y,

R ₁ -S- C

N-Y Y,

IO

To -H

(13)

R ₄ -C

NY ₄

N-Y,

Y «,

At

(11

in which an unsubstituted alkyl group having S to 18, preferably 12 to 18 carbon atoms, and Yq, Y ₁₀ and Y ₁₁ are each independently hydrogen. a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, a cycloalkyl or aralkyl radical, especially the cyclohexyl or benzyl radical, where Y ₉ and Yn together with the group

also the remainder of a partially saturated ring, especially a diazoline or tetrahydrodiazine ring, can form and An has the meaning given and preferably the chloride or bromide ion means.

Methvlsulfat quaternized adduct of 15 to 20 moles of ethylene oxide with N-octadecyl-diethylenetriamine.

7. Compounds of the formula

in the Y ₄ , Y ₅ and Y ₆ each independently

Hydrogen, one optionally substituted by hydroxyl Ν -

or lower alkoxy groups substituted lower /

Alkyl radical, a cycloalkyl or an aralkyl group, - C

especially the cyclohexyl or benzyl radical, represent \

and R ₄ and An® have the meaning given. 25 N -

Examples of suitable compounds of the formula II

are: Heptadecenyl-amidinium chloride, Undecyl-N-benzyl-amidinium chloride, Heptadecyl-N, N, N'-trimethyl-amidinium-methosulfate and heptadecyl-N-y-methoxypropyl-amidinium chloride.

Salts according to the definition of N-substituted derivatives of dodecyl, tetradecyl, octadecyl, octa

decenyl-ethylenetriamine, -propylenediamine, -diethylen- As examples of suitable compounds of formula 13

triamine, -dipropylenetriamine and -tetraäthylenpent- may be mentioned: Salts of S-dodeamine according to the definition, such as the dichlorohydrate of N-dodecyl-N-methyl-isothiourea, S-octadecyl-N.NYN'-tripropylthyl-N'.N'-dimethylpropylenediamine, or one with di-isothiourea, S-dodecyl-N-benzyl-isothiourea. S-dodecyl-N-cyclohexyl-isothiourea and S - octadecyl -N -; ■ - methoxypropyl - N '.N' - dimethylisothiourea.

40 An example of a compound of formula 4 is S-dodecyl - S - methyl - S - β - hydroxyethyl - sulfonium-NY-Γ methosulfal.

/ ' In the foregoing the expression "down" means

R ₃ -NH-C An (12) in connection with alkyl or alkoxy groups

\ 45 usually a remainder with no more than 4 carbon

NH-Y ₈ -J- H atoms of matter. Under higher alkyl radicals are in the

Usually radicals with about 8 to 22 carbon atoms verin the R _{3 was} an unsubstituted alkyl group with 8 to. In the process according to the invention, 18, preferably 12 to 18 carbon atoms and Y _{7 can} also be used as mixtures of cation-active compounds Y _8, independently of one another, per hydrogen or 50 bonds.

an optionally by hydroxyl or lower sub-compounds of the formulas 6 to 13

· ■ · ■ "- ■ ^J ·» - «- * those of formula 6 are particularly preferred

The cation-active compounds according to the definition are used in amounts of 2 to 10 percent by weight based on the weight of the fiber material to be treated.

The aqueous preparation that can be used according to the invention optionally contains that for the printer of fiber material made of polyacrylonitrile or poly δο acrylonitrile copolymers customary thickeners, such as on closed rubber types, e.g. B. so-called "crystal rubber", or cellulose-based thickeners, such as Jo hannis bread flour, galactomannans, tragacanth, British gum, polysaccharides or cellulose derivatives

may be mentioned: N-octadecyl-guanidine chloride, 65 such as methyl cellulose or soluble salts of the carboxy N-hexadecyl-N'-methyl-N ^ / i-hydroxyethyl-guanimethyl cellulose. Preference is given to thickeners in dinium chloride and 2-octylamino-imidazolinium carob gum and galactomannans.
acetate. For the purpose of setting the desired pH values

Alkoxy groups represent substituted lower alkyl, where Y ₇ and Y ₈ together with the group

- C

N-

NH

can also form the remainder of a partially saturated ring, especially a diazoline or tetrahydrodiazine ring, and An ^{e has} the meaning given. Examples of suitable compounds of the formula

21 24 61?

The aqueous preparation which can be used according to the invention can be mixed with conventional auxiliaries, especially organic acids such as formic or acetic acid, buffer substances such as ammonium or alkali metal salts, t. B. ammonium, sodium or potassium acetate, propionate or citrate, and optionally neutral salts such as sodium sulfate or sodium chloride, to be set.

As fiber material made of polyacrylonitrile or of polyacrylonitrile copolymers, the known types of fiber are used. If it is polyacrylonitrile copolymers, then is the acrylonile fraction at least 35 percent by weight and preferably at least 80 percent by weight of the copolymer. In addition to acrylonitrile, the comonomers used are normally used other vinyl compounds, e.g. B. vinylidene chloride. Vinylidenecyanide, vinyl chloride, methacrylate, methylvinylpyridine, N-vinyl-pyrrolidone, vinyl acetate, vinyl alcohol or styrene sulfonic acids.

This fiber material can be pretreated or dyed in any processing stage, so z. B. in the form of loose material, roving, yarn or knitted goods, such as knitted fabrics, woven fabrics or nonwovens as well as textile floor coverings such as woven, tufted or matted carpets,

As cationic dyes for dyeing the polyacrylonitrile fiber material pretreated according to the invention or polyacrylonitrile copolymers together with untreated polyacrylonitrile fiber material the usual compounds known under this name can be used. It is about chromophoric systems, the cationic character of which is derived from a carbenium, ammonium, oxonium or sulfonium grouping and which are present as water-soluble salts. Examples of such Cationic dyes containing chromophoric systems are arylazo-. Anthraquinones methine, azamethine, Azine, oxazine. Thiazine, xanthene, acridine, Polyarylmethane and coumarin dyes.

According to the invention pretreated fiber material made of polyacrylonitrile or polyacrylonitrile copolymers can if desired - ■ using appropriate fiber-affine dyes - not only together with untreated polyacrylonitrile fiber material. but can also be processed and dyed with other untreated fiber materials. For this come in particular Fiber materials made from linear, high molecular weight Esters of aromatic polycarboxylic acids with polyfunctional alcohols, such as polyethylene glycol terephthalate fibers, and synthetic polyamide fiber material as well as the corresponding acid modified Fibers into consideration. Here z. B. by dyeing fiber mixtures from pretreated polyacrylonitrile fibers, untreated polyacrylonitrile fibers and unmodified polyester or synthetic Polyamide fibers with a combination of the above-mentioned cationic dyes and conventional disperse dyes particularly interesting multi-color effects are achieved. The coloring of such fiber mixtures can also be done so that first with dispersion and then with cationic Dyes is colored. Such disperse dyes can belong to any class of dyes: these are mainly azo dyes or anthraquinones, nitro, methine, Styryl, azastyryl, naphthoperinone, quinophthalone, or naphthoquinone imine dyes.

The pretreatment of the fiber material made of polyacrylonitrile or polyacrylonitrile copolymers with the aqueous preparation, optionally containing thickener, of a cation-active compound according to the definition can be done according to the usual methods for dyeing or printing acrylonitrile fiber material, so z. B. after the so-called exhaust process in a long liquor (liquor ratio about 1:10 to 1: 50), if necessary under pressure

ίο temperatures between 85 ⁰ C and about 110 ° C, preferably 95 to 1 IOC, for 30 to 180 minutes; by impregnation, especially padding, e.g. B. in the form of tops, at temperatures below 80 'C, especially at 30 to 40 ⁰ C, and subsequent heat treatment, such as steaming, preferably with neutral saturated steam and optionally under pressure, at temperatures of for example 98 to 140 C for 3 to 30 minutes; or finally also by printing, such as roller blind printing, and subsequent steaming, preferably under pressure at temperatures of about 105 to 140 ° C. for 3 to 30 minutes.

The fiber material pretreated in this way is then expediently rinsed with warm and cold water and dried and then dyed together with untreated fiber material made of polyacrylonitrile or polyacrylonitrile copolymers in a manner known per se with at least one cationic dye. The dyeing is preferably carried out from aqueous liquor by the exhaust process (liquor ratio about 1:10 to 1:50) at temperatures of about 85 to 110 ° C with the addition of customary dyeing auxiliaries, such as organic acids, especially acetic acid, in order to adjust the pH Fleet made between 3.5 and 5th. The fiber material can, however, also be dyed continuously, ie by impregnation with a conventional dyeing aid, such as dye carriers and acid, and subsequent heat treatment, especially steaming at temperatures of about 98 to 105 ^° C.

Depending on the type of pretreatment and combination of according to the invention> 3 pretreatment is obtained with untreated fiber material made of polyacrylonitrile or polyacrylonitrile copolymers and optionally other untreated fiber material very effective two-tone and multi-tone effects. According to the invention pretreated fiber material can be stored and processed at any time and in the desired color shades, eliminating the need for costly warehousing of large quantities of pre-colored Materials are not required. The method according to the invention also makes it possible to simulate fiber material It is easy to dye quality in different shades, which is especially important when making carpets is of great importance because damii carpets can be produced with regard to Stability and shine of the pile a balanced: show picture.

. example 1

In a pretreatment bath containing 2.5 g of octadecyl amine acetate, 2 ml of 40% acetic acid and 1 g of sodium contains acetate dissolved in 1000 ml of water, 50 j Polyacrylonitrile yarn (e.g. Orion 42 yarn) introduced. The temperature of the liquor is increased below stan digcm move the textile material within about 30 minutes to the boiling point and boil

for 90 minutes. The treated acrylonitrile yarn is then cut into one on a knitting machine

Delte polyacrylonitrile yarn rinsed with warm water processed tricot.

and then dried. The knitted fabric prepared in this way is now on a!

The pretreated 50 g of polyacrylonitrile yarn fresh bath, which in 2000 ml of water 1.25 g de

are together with 50 g of untreated poly-5 dye of the formula

CH ₃ O

CH, C ₂ H ₅

CHXH ₁ OH

ZnCl.,

non

4 ml of 40% acetic acid and 10 g of crystalline. Contains sodium sulfate for 60 minutes at boiling temperature colored. The dyed material is then treated with lukewarm and then with cold Rinsed with water and dried.

In this way, a knitted fabric is obtained which shows a clear light blue / dark blue two-tone effect. The following color distribution was determined by reflection measurement: That according to the above specification pretreated polyacrylonitrile thread has absorbed 8% of the total absorbed dye; the untreated polyacrylonitrile yarn portion accounts for 92% of the absorbed dye.

In the above example, if the 2.5 g of octadecyl amine acetate are replaced by the de in the second column Table I below, the amounts of the pretreatment listed in the third column. * medium and carries out both the pretreatment and the dyeing in compliance with those described in Example 1 Conditions through, one obtains similar light blue / dark blue effects on the knitted fabric.

The dye components absorbed by the pretreated and untreated fibers go up. columns 4 and 5.

Table 1

Example No. Amount in g of preparation agent Absorbed dye 111 "i>

vorbchandcltcs unbchamiclk's Polyacrylic polyacn 1-

niirilgam ntlriljütrn

i.j

he 96

2.5

CH ₃ - N - (CH ₂ CH, O | _{T |} H

CH ₂

ί CH ₂

CH ₃ N - (CH ₂ CH ₂ O) _X, H

CH,

CH,

(CH ₂ CH ₂ O) ^ H

CH ₃ - N

(CH ₂ CH ₂ O) ^ H χ, + X ₂ + x ₃ + .V ₄ ~ 20

3 SQ ₁ CH ₃ -

80

2.5

C ₁₇ H ₃₃ - ^

CH, CH, OH

CH ₃ COO-

86

continuation

Example No. Menyc in - Preventive Medicine

Absorbed dye in%

pretreated »unbchandelles
Polyacrylic polyaeryl

nitrile yarn nitriljiarn

2.5

CH ₂

CH

CH,

94

Cl

i /
CH,

Example 6

1 kg of polyacrylonitrile flakes (Orion 42) are placed in a dyeing machine. Separately, a liquor is prepared which contains 30 g of octadecylpyridinium chloride, 40 ml of 40% strength acetic acid and 20 g of sodium acetate dissolved in 15 l of water. This pretreatment liquor is now pumped into the dyeing machine. The temperature of the liquor is then increased to the boiling point over the course of 20 minutes and then boiled for 90 minutes. The pretreated polyacrylonitrile flake is then rinsed with warm water, spun off, dried and then spun into a carpet yarn. The carpet yarn thus obtained, which has a low affinity for cationic dyes, is then processed into a carpet together with 1 kg of untreated polyacrylonitrile yarn of the same quality using a tufting machine. A piece of this carpet weighing 1 ks is now pulled into a reel runner and sewn at the ends. Now is allowed to dyed material 301 of water at 40 ⁰ C and run 100 sets crystalline g. Sodium sulfate too. Separated in 4 liters of water, which contain 40 ml of 40% acetic acid, 10 g of the dye of the formula

CH ₃ O

= N-N

NaCl,

(102)

2 g of the dye of the formula

CH ₃ N-CH ₂

CH,

and 1.5 g of the dye of the formula

CH ₃ O

SO ₄ CH,

(103)

N = N

solved. The dye solution obtained is then carefully added to the dye liquor. Then increased the temperature of the liquor is raised to 95 ° C. in the course of 45 minutes and then dyed for 60 minutes with a gentle boil. Then the dyed carpet is first covered with warm and then with Rinsed in cold water and dried. You get

C ₂ H ₅

CH ₂ CH ₂ OH

ZnCl ₃

(104)

in this way a carpet with light brown and dark brown patterns.

The following color distribution was determined on the basis of reflection measurements: On the pretreated Polyacrylonitrile yarn portion has absorbed 4% of the total absorbed dye; ouch the unbundled polyacrylonitrile yarn portion

609 521/42 <

/ IO

18th

96% of the total absorbed dye

St Oil CS * iww ··· ». - - - j *

Similar effects are obtained when used on Dralon or Exlan.

B e i s ρ i e! 7th

treatment agent uema J Example X shows the previous ίο "'• ■ ψ-" ■■ - "-" 7 ",,,, -..".

Treatment otherwise as described in Example 6 stoffgem.sch, consisting of 6 g of the har ^ offes

through and colors the through processing of the treated formula
Delten and untreated fiber material obtained

ZnCl.,

111) 51

and 6 g of the dye of the formula
CH, O

N = N

N
CH ₃

CH,

CH ₁ CH ₁ OH

ZnCl.,

(106)

is used, a light green / dark fiber content is obtained, accounting for 19%. on the untreated green colored carpet. The reflection measurements accounted for 81% of the total recorded color donations the following values: On the pretreated fabric.

Example 8

If, in Example 6, 50 g of the pretreatment agent are used instead of the 30 g of octadecylpyridinium chloride the formula

CH ₃

C ₁₂ H ₂₅ -N

CH,

CH ₃

Cl

(107)

, performs the pretreatment as in Example 6 Toggle material in compliance with the beschriegegeben in Example 6 and then stained in the same manner bencn the color conditions with a Farbstoffge-? \ i a carpet processed Polyacrylnitrilfaser- 6o mixture consisting of 4 g of the dye the formula

CH ₁ O

CH.,

NO,

CH,

Cl

(1081

end 8 g of the dye of the formula

CH ₁ SO ₄

(109)

so you get a carpet, which

a) from intensely scarlet colored untreated Polyacrylonitrile yarn and

b) from a pale yellowish red colored pretreated Composed of polyacrylonitrile yarn.

The ratio of the treated and untreated polyacrylonitrile fiber material absorbed Dye is 20:80.

Example 9

If the pretreatment of the polyacrylonitrile flakes is as described in Example 6, but using of 50 g of the quaternization product of N-Dodecy! -N, N-dimethylamine with epichlorohydrin Place the 50 g of octadecyl "pyridinium chloride used in Example 6 and then carried out in Fiber material processed in the same way into a carpet, consisting of equal parts pretreated and untreated polyacrylonitrile yarn in compliance with the dyeing conditions described in Example 6 with 5 g of the dye of the formula CH-,

, J-N = N-T

NH

ZnCl ₃ (110)

colored, you get a patterned carpet, which is

a) made of intensely yellow-dyed untreated polyacrylonitrile yarn and

b) made of pale yellow colored, pretreated polyacrylonitrile yarn composed.

The reflection measurement results in the following color distribution: On the pretreated polyacrylonitrile fiber portion, 9% of the total absorbed Amount of dye absorbed; the untreated portion accounts for 91% of the total dye.

example

A printing paste containing 50 g 1 of the pretreatment agent of the formula

(111)

5 g / l locust bean gum thickener and 5 ml / l 80% acetic acid are applied to a fabric consisting of polyacrylonitrile fibers using a roller printing machine. The liquor application is 100% printing paste, based on the dry weight of the fabric.
The fabric printed with this pretreatment agent is then ^{steamed for 15 minutes at a temperature of 120 °} C. and 1 atm, whereupon the steamed material is rinsed with warm water and dried.

A piece of this pretreated polyacrylonitrile

fiber fabric weighing 1 kg is now pulled into a reel runner and sewn at the ends.

Now allowed in the winch 35 1 of water at 4O ⁰ C

run in and use 100 g of crystalline. Sodium sulfate too. 3 liters of water are added separately with 40 ml of 40% igei

Acetic acid is added, whereupon 10 g of the dye: the formula

J 1

O ₂ N- <f VN = N- <

CH ₂ CH ₂ -N

Cl

(112)

admits. The dye solution prepared in this way is now carefully added to the liquor. The temperature of the dyebath is then increased to 95 to 97 ° C. over the course of 50 minutes. It is then dyed for one hour while boiling gently. In this way, a color print is obtained in which the areas printed with the pretreatment agent are pale red. the unprinted areas, on the other hand, are colored intensely red.
In this example, if you replace the 50 g preparation of the formula

Cl

(11?)

by the same amount of one of the Vo listed in Table II below in the second column treatment agent and is used for both pre-treatment and subsequent dyeing As described in Example 10, a color print with a pale red, intense red pattern is also obtained

Table II Example No.

21

Pretreatment agent
C ₁ H,

C ₂ H ₅
CH ₁ CH ^ OH

22nd

he

CH ₂ CH ₂ OH j ^T

C ₁₈ H ₃₇ -N

CH ₂ CH ₂ OH J

C ₁₈ H ₃₇ - n ^ y + - π HCOO "

CH ₃ CH ₂ - CH O (CH, CH ₂ O) _Xi H

C "H" —N

CH ₂ -CH-O (CH ₂ CH ₂ O) ^ h

CH ₃ (CH ₂ CH ₂ O) _x , HI ⁺

H Cl

C, _H H "-N

CH ₂ CH - _{O (CH 2} CH ₂ O) ₁₂ H

CH ₃

CH ₃ SO ₄

CH, CH, CN

C, hH "-N

CH ₂ CH ₂ CH CH ₂ -CH ₂ -OCH,

Br "

CH ₃

C ₁₁ H ₂₃ CONH (CH ₂ ), -N

CH,

CH,

CI

C ₁₈ H ₁₅ OCH ₂ CH ₂ CH, N (CH,),] 'CH ₁ SO ₄

x, + X ₂ =

.V. + X ₂ =

continuation
Example no.

23

Vorbchandlunpsmillcl

C ,, H,., CONH (CH,) ₂ N 43

CH ₅

- H CT

C _IH H, -

CH,

Cl

-N>

Cl

C ₁₇ H ₁₅ C

CH,

N-CH,

N-CH ₂ CH ₂ CH ₂ OH

N-CH ₂ CH ₁ SO ₄

N-CH, -H CT

N - CH,

C ₁₇ H ₃₃

CH, -

/ NH-CH ₂ -H Cl '

N-CH,

CH ₃ -C

-H Br "

N-CH,

ί
C ₁₈ H ₃ , J.

CH ₃
N-CH ₂

CH ₁ -C

CH, so;

continuation
Example no.

25th

Pre-bundling agents -CH,

N-CH,

CH, -C "'CH,

N-CH, Cl

N-CH

// CH

N-CH

C] ₂ H ₂₅ Cl

CH,

CH-C

/ CH ₃

CH ₃ N-CH

N-CH CH ₃ SO ₄ -

NH H Cl

C ₁₁ H ₂₃ -C

NH ₂ NH

NH-CH ₂

N-CH ₃

C ₁₇ H ₃₅ -C CH ₃ -

H CHjSO ₄ -

NH

C, ₇ H "-C-H CV

NH <CH ₂ ), OCH, CH ₃ CH, 1 ⁺

Q ₄ H ₂₄ -N-CH ₂ CH ₂ -N-CH,

CH ₃ CH ₃

/ If

2CH ₁ SO ₄ -

continuation

Example no.

27

Pretreatmentliinysmiuel

CH ₁ CH ₁ OH

CH ₁ CH ₁ OH

C _n H ^ -N-CH ₁ CH ₁ CH ₁ -N

CH ₂

CH ₂

1.

CH ₁ CH ₁ OH

2Cl

(CH ₂ CH ₂ O) _x H (CH ₁ CH ₇ O) ^ H

C ₁₇ H ₃₅ -N CH ₂ CH ₂ N CH ₂ CH ₂ -

X ₁ + x ₂ + χ, + x ₄ = NH (CH ₂ CH ₂ O) ^ H

(CH ₂ CH ₂

C _1x H ₃ , -NH -C

-H Cl

NH ₂

N-CH

C ₁₁ , H ₃₃ -NH-C

NH-CH ₁ CH ₁ OH -H Cl

N-CH ₁

QH ₁₇ -NH-C

NH-CH ₂ NH H CH ₃ COO "

Cj ₂ H ₂₅ SC

H Cl "

₁₂ H ₁ *;

NH ₂ NH

NH-CH, -

NH

<Ή

// X -H Br "

-H Cl "

C ₁₂ H ₂₅ S

CH ₁ CH ₁ OH

CH ₃ SQT

If in Example 1, instead of the 2.5 g of octadecylamine acetate, the same amount as in the previous examples 10 to 43 given pretreatment agent, the pretreatment performs as described in Example 1 and then dyes the knitted fabric produced in an analogous manner untei If the conditions given in Example I are met, knitted fabrics are obtained which are similar to one another has a good light blue dark blue two-tone effect.

Example 44

In a pretreatment bath containing 1.5 g of the pretreatment agent of the formula

Fc ₁₈ H ₁₇

Cl

(114)

Contains 2 ml of 40% EsMgic acid and 1 g of sodium acetate dissolved in 1200 ml of water, 50 g of poly- »Acrylonitrile yarn introduced. The liquor temperature is now increased by constantly moving the textile material within 30 minutes to 95 C and ίο then cooks for 90 minutes. That treated Polyacrylonitrile yarn is then rinsed with warm water and dried.

Now 50 g of untreated polyacrylonitrile garri are added together with the in the manner described above is pretreated polyacrylonitrile yarn on a knitting machine processed into a jersey.

In a fresh bath, which in 2000 ml of water 0.5 ρ of the dye of the formula

O, N

N = N

4 ml of 40% acetic acid and 10 g of sodium sulphate in solution, the knitted fabric is now used for 60 minutes colored at boiling temperature. The material to be dyed is then washed with warm and then with cold water rinsed and finally dried.

In this way, a knitted fabric is obtained which has a pale yellow-brown / intense yellow-brown two-ion effect shows. The following color distribution was determined by means of reflection measurements: The one on the one described Well-pretreated polyacrylonitrile yarn anicil has 9% of the overall color oil

(115)

C ₂ H ₅

"CH ₂ CH ₂ N (CH,)
NH ₂

absorbed substance: 91% of the total absorbed dye is attributable to the untreated antci.

polyacrylonitrile yarn according to the specifications of the Example 44 pretreated and processed with untreated polyacrylonitrile yarn, and is used for dyeing of the manufactured knitted fabric instead of the 0.5 g of the dyes given in Example 44 above 1 g of one of the dyes listed in column 2 of Table III below is used in each case knitted fabric dyed in the shades given in columns 3 and 4.

Table III

At- dye

Color shade on polyacrylic paper
pretreated unbchandcll

₂ N- ^ Vn = n

Cl

46 CU

f> - N =

CH ₅

C ₂ H ₄ O

C ₂ H ₅

C ₂ H ₄ -N er

Cl "

bright blue tinted red

pale yellow brown

deep bluish red

Intense cel brown

O NH (CH,)., N (CH,). J

CH ₃ SO ₄ -

black blue intensive blue

continuation

At- FarbvtorT

Color oi? on polyacrylic yarn
pretreated untreated

-1 "5

CH = CH-

■ N

CH

-2 ^1J 5_J

ZnCl ₃ "pale pink, intense red

CH ₃ SO ₄ "

pale yellow intense yellow

OCH,

CH,

C ₂ H ₅ N (CH,)., Er

light brown

dark brown

Light Blue

intense blue

Example 52

300 g of polyacrylonitrile yarn in the form of a cross-wound bobbin are placed in a closed laboratory paint machine brought in. A pretreatment liquor is separated, which in 4.5 l of water contains 30 g of the pretreatment agent of the formula

The textile material 45 by increasing the temperature of the dye bath within 15 minutes 6O ⁰ C.

Separately, 26 g of a dye off preparation are in about 500 ml of water. which the dye of formula

fc, ₇ H "CONH (CH ₂ ), N (CH ₃ )

p ^: H

Cl-

(116)

CO-N

Contains 12 ml of 40% acetic acid and 6 g of sodium acetate. Now letting this pretreatment liquor in the dyeing machine run in, the temperature was raised within 45 minutes at 105 to 107 ⁰ C and kept at this temperature for 90 minutes. It is then cooled to room temperature, the material to be dyed is rinsed with warm water, spun off and then dried.

The polyacrylonitrile yarn pretreated in this way is now used together with 500 g of untreated polyacrylonitrile yarn and with 500 g of yarn made of polyethylene glycol terephthalate on a knitting machine to form a knitted piece processed.

The knitted piece made in this way is now drawn into a reel runner. 40 l of water are then run in and 80 g of an emulsion of the sodium salt of o-phenylphenol and 80 g of diammonium sulfate are added as swelling agent. While constantly moving the CH ₃ O

N = N-CH
\

CO-N

CO (117)

CH,

contained in finely divided form, slurried. The received Dye dispersion is now carefully added to the dye liquor, whereupon the temperature is set the liquor increased from 60 to 95 ° C within 30 minutes. It is then dyed for 90 minutes with a gentle boil. The material to be dyed is then rinsed with hot water, then soaped and again rinsed with water.

The overcolouring of the treated and the untreated Polyacrylnilrilgarn-Anleils is then made as follows:

Another 40 l of water at 40 ° C. is allowed to run into the reel vat and 100 g of crystalline are used. Sodium sulfa IU Separately in 5 l of water, we.chc J- ml of 40% acetic acid contain Π g of the dye of the formula

CH ₅

C!

(118)

solved. The dye solution obtained is now carefully added to the dye liquor. The temperature of the liquor is then increased within an hour 95'C and then stains for 60 minutes with a gentle boil, whereupon the knitted piece is knitted Rinsed with warm water, spun off and then dries. Subject to the above conditions you get a piece of knitting, which is

a) made of greenish yellow-dyed polyethylene glycol terephthalate yarn,

b) made of hay-green dyed, pre-treated polyacrylonitrile yarn and

ο made of intensely bluish green colored untreated Composed of polyacrylonitrile yarn.

Claims (1)

21 24 6ι7 Patent claims: 1. Process for producing multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copolymers by applying an aqueous preparation, optionally containing thickener, of an uncolored, cation-active, at least an organic compound containing a higher alkyl radical, followed by dyeing with a cationic dye, thereby characterized in that one fiber material made of polyacrylonitrile or polyacrylonitrile copolymers with the aqueous preparation at temperatures of at least 85 ° C and a pH value between 3 and 5 pretreated and the pretreated material together with untreated Dyes fiber material made of polyacrylonitrile or polyacrylonitrile copolymers and that the aqueous Preparation 2 to 10 percent by weight, based on the weight of the fiber material to be treated, on a cationic compound of the formula 15th R ₁ - (CO-NH- (CH ₂ ) ,,), -! - N-X ₂ V ₁
N At (1) R ₂ -C At (2) 35 40 NY ₁ NY ₂ 1 Y ₃ To (3) -H R ₃ -S W, W, CH ₃ SO ₄ (4) 55 60 contains where R _{1 is} an alkyl radical having 8 to 18 carbon atoms, X ₁ and X _{2 are} each hydrogen, lower alkyl, cycloalkyl or a polyalkylene glycol radical which may be substituted by hydroxyl, lower alkoxy or cyano, or X, and X ₂ together with the nitrogen atom connecting them Piperidine or morpholine ring, X ₃ hydrogen, optionally through hydroxy! or lower alkoxy-substituted lower alkyl or aralkyl, or X ₁ , X ₂ and X ₃ together with the nitrogen atom connecting them a pyridine ring optionally substituted by lower alkyl, one of the radicals R ₂ , V ₁ and V _{2 is} an alkyl group with 8 to 18 Carbon atoms and the other hydrogen, alkyl or aralkyl optionally substituted by hydroxyl, Z is a saturated or unsaturated alkylene radical with 2 or 3 carbon atoms, Yi, Y ₂ and Y _{3 are} each hydrogen, lower alkyl, cycloalkyl or aralkyl optionally substituted by hydroxyl or lower alkoxy, Q is sulfur or —NH-, r and s each 1 or 2, η 2 or 3, An ^i; is an organic or inorganic acid, R _{3 is} an unsubstituted alkyl group having 8 to 18 carbon atoms and W ₁ and W _{2 are} each optionally lower alkyl which is optionally substituted by hydroxyl. 2. The method according to claim 1, characterized in that mm is a cationic compound the formula R ₁ -NX ₂
X3 At (5) used, wherein R ₁ , X ₁ , X ₂ , X ₃ and An have the meaning given in claim 1. 3. The method according to claim 2, characterized in that that you have a cationic compound of the formula R.3 N X5 At (6) used, where X ₄ . and X ₅ independently of one another each hydrogen, a lower alkyl radical optionally substituted by hydroxyl, lower alkoxy or cyano, a cycloalkyl radical or a polyglycol ether chain with 2 to 40 alkyleneoxy groups or X ₄ and X ₅ together with the nitrogen atom connecting them a piperidine or morpholine ring, X ₆ hydrogen, an optionally represents a lower alkyl radical substituted by hydroxyl or lower alkoxy groups or an aralkyl radical and R ₃ and An have the meaning given in claim 1. 4. The method according to claim I, characterized in that that you have a cationic compound of the formula - CO - NH-iCH ₂ ) "- N - X ₇ To (7) used, in which R _{4 is} an unsubstituted alkyl group with II to 17 carbon atoms and X ₇ and X _{h are} each an unsubstituted lower alkyl group and / 1 and An have the meaning given in claim 1 and Χ ,, have the meaning given in claim 3. 5. The method according to claim 1, characterized in that there is a cationic compound the formula 8. The method according to claim 1, characterized in that there is a cationic compound the formula -R. At (8th) used, wherein R _{5 is} an unsubstituted or interrupted alkyl group with 8 to 18 carbon atoms, R _{6 is} hydrogen, methyl, ethyl and An is the anion of an organic or inorganic acid. 6. The method according to claim 1, characterized in that that you have a kaiionische compound of the formula 20th (CH ₂ J ₁₁ CR ₇ At- (9) used, wherein one of V ₄ and R _{7 is} an unsubstituted alkyl group having U to 18 carbon atoms and the other is hydrogen or a lower alkyl radical optionally substituted by hydroxyl groups, V _{3 is} hydrogen and - if V ₄ or R _{7 is} not hydrogen - also one is a lower alkyl radical optionally substituted by hydroxyl groups or an aralkyl radical and η and An ^{3 have} the meanings given in claim 1. 7. The method according to claim 1, characterized in that that you have a cationic compound of the formula CH-N CH-N On ₁ (10) 55 6ο used, in which V _{5 is} an unsubstituted lower alkyl group or the benzyl radical and V _{h is} an unsubstituted alkyl group with 12 to 18 carbon atoms, R _{8 is} hydrogen, an unsubstituted alkyl group with up to 18 carbon atoms or the unsubstituted phenyl radical and An, the anion of hydrochloric or hydrobromic acid or which means methylsulfuric acid. N-Y, R ₄ -C N- ' At
H (11) used, wherein Y ₄ , Y ₅ and Y ₆ are each independently hydrogen, a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, a cycloalkyl or aralkyl group and R ₄ and An have the meaning given in claim 4. 9. The method according to claim 1, characterized in that there is a cationic compound of the formula R ₃ -NH-C N-Y. NH At
-H 02) used in which Y ₇ and Y ₈ each independently represent hydrogen or a lower alkyl resi optionally substituted by hydroxyl or lower alkoxy groups, Y ₇ and Y ₈ together with the group N - NH- can also form the remainder of a partially saturated ring and R ₃ and An 'hold the meaning given in claim 1. 10. The method according to claim 1, characterized in that that you have a cationic compound of the formula R ₃ -SC At -H (13) NY ₉ Yn used, in which Y ₉ , Y ₁₀ and Y ₁₁ are each independently hydrogen, a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, cycloalkyl or aralkyl radical. especially the cyclohexyl or 5 \
N -
I. 2 1 24 6th 1 7th Ψ 6th Benzyl radical, where Y ₉ and Y ₁₀
with the group
N - I. together ] ·
N - C R ₇ -C ^ \
Z \ /
N
I. I.
V ₂ At audr can form the remainder of a partially saturated ring and R ₃ and An ^{s have} the meaning given in claim 1. From the German Auslegeschrift 10 76 079 it is known, reservation effects on structures such as Woven and knitted fabrics made from hydrophobic fibers, including polyacrylonitrile fibers. to generate by the textile material is treated with a printing paste containing an aromatic, mphoteric compound and then colors. The result of a pretreatment with such compounds on polyacrylonitrile fibers and then dyeing the treated with untreated polyacrylonitrile fibers However, the samples obtained did not show the desired, differentiated, but practically the same color Colorations. Furthermore, from the German Auslegeschrift 11 48 971, column 4, lines 13 to 25 are quaternary ammonium salts known which contain at most one cyclic radical and one fatty alkyl radical in the molecule. These cationic compounds are used there as leveling agents for dyeing polyacrylonitrile fibers described together with the dyes. However, these tools show when used directly in the dyebath strong blocking effects and a poor leveling capacity, so that insufficient Colorations can be generated. A process has now been found which allows it by applying an optionally thickener containing aqueous preparation of an uncolored, cation-active, at least one higher Suitable organic compound containing an alkyl radical and subsequent dyeing with a cationic Dye on fiber material made of polyacrylonitrile or polyacrylonitrile polymers strong dyeings to produce, which have an excellent strongly contrasting multi-tone effect and also don't care. The method is characterized in that one fiber material made of polyacrylonitrile or polyacrylonitrile copolymers with the aqueous preparation at temperatures of at least 85 ° C and a pH value between 3 and 5 pretreated and the pretreated material together with untreated Dyes fiber material made of polyacrylonitrile or polyacrylonitrile copolymers and that the aqueous Preparation 2 to 10 percent by weight, based on t> o based on the weight of the fiber material to be treated, of a cationic compound of the formula