DE2124617A1 - Process for creating multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copolymers - Google Patents

Description

ClBA-GEIGY AG, CH-4002 Basel I ** IQ f ^ "~ % 3 CSijl Ϊ

2124S17

Case 1-3314 / E

Process for creating multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copoly-

meren

The present invention relates to a method for producing multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copolymers and the fiber material thus dyed in different shades. *

It has already been proposed to create reservation effects on structures, such as woven and knitted fabrics, from hydrophobic Fibers, including polyacrylonitrile fibers, to be produced by treating the textile material in places with an aromatic amphoteric compound-containing printing paste treated and then colored. Those with such connections However, the effects that can be achieved by polyacrylonitrile fiber material have proven to be inadequate.

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It has now been found that one can easily produce effective contrasting multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copolymers by mixing fiber material made of polyacrylonitrile or polyacrylonitrile copolymers with an aqueous preparation, optionally containing thickener, of an uncolored, cationic organic ammonium containing at least one higher alkyl radical - Or sulfonium compound at temperatures of at least 85 ⁰ C, preferably ^{95-110 0} C, and a pH value between 3 and 5, in particular between 4 and 4.5, pretreated and at least one such pretreated fiber material together with untreated fiber material made of polyacrylonitrile or Dyes polyacrylonitrile copolymers with at least one cationic dye.

The preferred procedure is to pretreat with an aqueous preparation which is cation-active contains organic ammonium compound which has an alkyl radical having 8 to 22 carbon atoms and their cationic part of the molecule only carries a single positive charge.

The use of cation-active organic ammonium compounds of the formula is of particular interest

(D

R ¹

R- (CO-NH- (CH ₂ ) _h ) _r-1 -% - R "

) Π I

208860 / 1149- »»

IV

R ° - C

(3)

.NO

- ^ s-I -

- R viii

vii

- H

R is an alkyl radical having 8 to 18 carbon atoms, R ¹ and R ″ are each hydrogen, optionally by hydroxyl; lower alkoxy or cyano-substituted lower alkyl, cycloalkyl or a polyalkylene glycol radical or

R ¹ and R "together with the nitrogen atom connecting them a piperidine or morpholine ring,

R "'is hydrogen, optionally by hydroxyl or lower Alkoxy substituted lower alkyl or aralkyl, or

R ¹ , R, "and R"'together with the nitrogen atom connecting them a pyridine ring optionally substituted by lower alkyl,

one of the radicals R °, R ^1V and R ^{V is} an alkyl radical having 8 to 18 carbon atoms and the other is hydrogen, optionally alkyl or aralkyl substituted by hydroxyl,

Z is a saturated or unsaturated alkylene radical with 2 or 3 carbon atoms,

BAD OFUG4NAL

209850/1149

R ^V "^ R ^{v: L: L} and R ^V111 each hydrogen, lower alkyl, cycloalkyl or aralkyl optionally substituted by hydroxyl or lower alkoxy,

Q sulfur or -NH,

r and s each 1 or 2,

η 2 or 3 and

X mean the anion of an organic or inorganic acid.

Good results are achieved above all with a cationic organic ammonium compound of the formula (I)

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

(4)

R-N- R "

where R, R ¹ , R ^M , R '"and X have the meaning given. Among the ammonium and sulfonium compounds to be used, the following 10 types of compounds have proven to be particularly interesting:
1. Compounds of the general formula

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(5;

R ₁ - ^ - R

^R 4 J

in the _

R _{1 is} an unsubstituted alkyl group having 8 to 18, preferably 12 to 18 carbon atoms,

R “and Ro, independently of one another, are each hydrogen, one optionally lower alkyl radical 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 ethyleneoxy groups, and optionally individual propyleneoxy or phenylethyleneoxy groups or

Rg and Ro together with the nitrogen atom connecting them a piperidine or morpholine ring,

R, hydrogen, a lower alkyl radical which is optionally substituted by hydroxyl or lower alkoxy groups or an aralkyl radical, especially the benzyl radical, and

X the anion of an organic or inorganic acid, such as the anion of the ant, vinegar, hydrogen chloride, Hydrobromic, sulfuric, phosphoric or methylsulfuric acid

represent.

As examples of suitable compounds of the formula (5)

may be mentioned: Salts of N-dodecyl-N- according to the definition

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cyclohexylamine, N-dodecyl-N-benzylamine, N-cyano-ethyl-N-dodecylamine, N, N-bis- (ß-hydroxyethyl) -N-dodecylamine, N, N-bis- (ß-hydroxyethyl) -N-octadecylamine, N-octadecenyl piperidine; of condensation products of dodecyl, tetradecyl, octadecyl and octadecenylamine with 2 to 40 moles of alkylene oxide, especially ethylene oxide, such as 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 (5) are: N-dodecyl-NjNjN-trimethylammonium methosulfate, N-dodecyl-NjN-dimethyl-N-benzylammonium chloride, N-dodecyl-NjN-diethyl-N-ß-hydroxyMethylammonium chloridej N- Tetradecyl-NjN-dimethyl-N-benzylammonium chloride, the reaction product of octadecylamine with 10 mol of ethylene oxide, quaternized with dimethyl sulfate, and the reaction product of dodecylamine with 7 mol of ethylene oxide, quaternized with epichlorohydrin.
2. Compounds of the general formula

(6)

R ₅ - CO - NH - (CH ₂ ) _n ■>% - R

in the ,

Rc is an unsubstituted alkyl group with 11 to 17 carbon atoms,

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Rg and Ry each represent an unsubstituted lower alkyl group and η mean 2 or 3 and

R and X have the meaning given.

Examples of suitable compounds of the formula (6) are the salts of compounds obtained by condensation of coconut oil fatty acid chloride with N, N-dimethyl propylenediamine and the salts of the quaternary compounds obtainable from these condensation products by reaction with dimethyl sulfate, glycol chlorohydrin, epichlorohydrin or benzyl chloride.
3. Compounds of the general formula

in the

Ro a possibly interrupted by oxygen atoms, unsubstituted alkyl chain with 8 to 18, preferably 12 to 18 carbon atoms and

R _{0 is} hydrogen, the Nethyl ^ group or Aethylgruppc and X has the meaning given.

As examples of suitable compounds of the formula (7)

may be mentioned: dodecyl pyridinium chloride, octadecyl pyridinium chloride, Dodecyl-3- or -4-methylpyridinium chloride and octadecyloxymethyl pyridinium chloride.

4. Compounds of the general formula

BAD ORlGiNAL

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(8th;

(CH ₂ )

- R

11

in the

of R, _Q and R ,. one R is an unsubstituted alkyl group with 11 to 18 carbon atoms and the other R is hydrogen or a lower alkyl radical optionally substituted by hydroxyl groups,

Hydrogen and - if R, ~ or R ,, not hydrogen

10 11

mean - also a lower alkyl radical optionally substituted by hydroxyl groups or an aralkyl radical, especially the benzyl radical, and η mean 2 or 3 and
X has the meaning given.

Examples of suitable compounds of the formula (8) are: 2-heptadecyl-imidazolinium acetate, 1- / 3-HydroxySthyl-2 »heptadecyl-imidazolinium chloride, 1-ß-hydroxyethyl-2-heptadecyl-3-methylimidazolinium-methosulr fat, l-undecyl-2-methyl-imidazolinium chloride and 2-heptadecenyl-tetrahydropyridinium chloride. 5. Compounds of the formula

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(9)

R CH © Ν

15th

CH-N

ι R

C-R

13th

in the

R, o is an unsubstituted alkyl group with 12 to 18 carbon atoms,

R, # hydrogen, an unsubstituted alkyl group with up to to 18, preferably 1 to 4 carbon atoms or the unsubstituted phenyl radical,

R _{15 is} an unsubstituted lower alkyl group or the benzyl radical and

Χ-, the anion of hydrochloric or hydrobromic acid or represent the methylsulfuric acid. Examples of compounds of the formula (9-0 are

called: l-dodecyl-S-benzyl-imidazolium chloride and 1-hexadecyl-2-isopropyl-3-methylimidazolium methosulfate. .

6. Compounds of the general formula

(10)

NO

- C

18th

7 - ^R 17 ^R 16

in the

Rc is an unsubstituted alkyl group having 11 to 17 carbon atoms and

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R, ry R ₁₇ and R-, ο each independently represent hydrogen, a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, a cycloalkyl or an aralkyl group, especially the cyclohexyl or benzyl radical, and X has the meaning given.

Examples of suitable compounds of the formula (11) are: heptadecenyl-amidinium chloride, undecyl-N-benzyl-amidinium chloride, Heptadecyl-Ν, Ν-, Ν'-trimethyl amidinium methosulfate and heptadecyl-N-7-methoxypropyl-amidinium chloride. 7. Compounds of the formula

(H)

R-,

N - (CH ₂ ) _n ^R 4

N -

(m + D®

in the

R, ο one optionally substituted by hydroxyl groups lower alkyl radical, especially the methyl radical, or a polyglycol ether chain with 2 to 40, preferably 5 to 20 alkyleneoxy groups, especially ethylsnoxy groups. and optionally individual propyleneoxy groups or phenylethyleneoxy groups,

η 2 or 3 and

m is an integer from 1 to 4, and R 1, R, and X have the meanings given.

Examples of suitable compounds of the formula (12) are:

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DefinitionsgemSsse salts of N-substituted derivatives of dodecyl, tetradecyl, octadecyl, octadecenyl-äthylentriamin, -propylendiamin, -diäthylentriamin, -dipropylentriamin and -tetraäthylenpentamin as the dihydrochloride of N-dodecyl-N-methyl-N ', N ¹ dimethylpropylenediamine, or an adduct of 15 to 20 mol of ethylene oxide with N-octadecyl-diethylenetriamine quaternized with dimethyl sulfate. 8. Compounds of the formula

(12) R ₁ -NH-C ^. ^2L X®

NH - R ₂₀ H.

in the

R, an unsubstituted alkyl group of 8 to 18, preferably 12 to 18 carbon atoms and

R _"n and R" each independently represent hydrogen or an optionally groups by hydroxyl or lower Alkox3 ^{7-substituted} lower alkyl group, wherein R _2n and R ₂ -, _n, together with the group -C, also. Rest of a partially saturated ring, especially a Diaüolin- or Tetrahydrodiazinringes, can form and

X has the meaning given.

As examples of suitable compounds of the formula (12)

may be mentioned: N-octadecyl-guanidinium chloride, N-hexadecyl-N ¹ -methyl ~ N ^fl -jß-hydroxyKthyl-guanidinium chloride and 2-octylamino-imidazolinium acetate.

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9. Compounds of the formula

(13)

- ^R

R ₁ -SC.

Έ - R

R,

-H

in the

an unsubstituted alkyl group of 8 to 18, preferably 12 to 18 carbon atoms and

R " ₂ ", R ₂ "and R _? , independently of one another for each hydrogen, a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, a cycloalkyl or aralkyl radical, especially the cyclohexyl or benzyl radical,
mean, where
R ₂₂ and R "o together with the group -C - ^^ also the rest

a partially saturated ring, especially a diazoline or tetrahydrodiazine ring

and
X has the meaning given and is preferably the chloride or bromide ion.

As examples of suitable compounds of the formula (1.3; may be mentioned: salts of S-dodecyl-isothiourea according to the definition, S-octadecyl-N, N ', N'-tripropyl-isothiourea, S-dodecyl-N-benzyl-isothiourea, S-dodecyl-N-cyclohexyl-isothiourea and S-octadecyl-N-y-methoxypropyl-M ', N'-dimethyl-isothiourea.

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- '13 -

10. Compounds of the formula

(14)

^R i -

CH

3 ^l

in the

R, an unsubstituted alkyl group having 8 to 18, preferably 12 to 18 carbon atoms and R "c and R ^ g each one optionally through hydroxyl groups substituted lower alkyl radical. An example of such a compound is S-dodecyl-S-methyl-S-ß-hydroxyethyl sulfonium methosulfate called .

In the foregoing, the term "lower" in connection with alkyl or alkoxy groups generally means a radical with no more than 4 carbon atoms. Higher alkyl radicals usually include radicals with about 8 to 22 carbon atoms Understood. Mixtures of cation-active compounds according to the definition can also be used in the process according to the invention be used.

Among the compounds of formulas (5) to (14) are those of the formula (5) are particularly preferred.

The cation-active compounds according to the definition are expediently used in amounts of at least 1 percent by weight , especially 2 to 10 percent by weight, based on the weight of the fiber material to be treated, used.

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The aqueous preparation which can be used according to the invention optionally contains those customary for printing fiber material made of polyacrylonitrile or polyacrylonitrile copolymers Thickeners, such as digested rubbers, e.g. so-called "crystal rubber", or cellulose-based thickeners, such as Locust bean gum, galactomannans, tragacanth, British gum, polyseccharides or cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose »Preference is given to thickeners made from locust bean gum and Galactomannans.

In order to set the desired pH, the aqueous preparation which can be used according to the invention can Usual auxiliaries, especially organic acids such as formic or acetic acid, buffer substances such as ammonium or alkali metal salts, e.g. ammonium, sodium or potassium acetate, propionate or citrate, as well as neutral ones if necessary Salts such as sodium sulfate or sodium chloride can be added.

As a bevel material made of polyacrylic «! tril b?; v ?. ?, ur. PcIy-acrylonitrile copolymers the commercially known types of fibers can be used. If it is polyacrylonitrile polymers is concerned, the acrylonitrile content is at least 35 percent by weight and preferably at least 80 Weight percent of the copolymer. Used as comonomers in addition to acrylonitrile, other vinyl compounds, e.g. vinylidene chloride, vinylidenecyanide, vinyl

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chloride, methacrylate, methyl vinyl pyridine, N-vinyl pyrrolidone, Vinyl acetate, vinyl alcohol or styrene sulfonic acids.

This fiber material can be pretreated or dyed at any processing stage, e.g. in the form of loose material, roving, yarns or knitted goods, such as knitted fabrics, woven or nonwovens and textiles Floor coverings, such as woven, tufted or matted carpets.

As cationic dyes for dyeing the invention pretreated fiber material made of polyacrylonitrile or polyacrylonitrile copolymers together with untreated Polyacrylonitrile fiber material can include the usual compounds known by this name are used. These are chromophoric systems, the more cationic Character comes from a carbenium, ammonium, oxonium or sulfonium grouping and is water-soluble Salts are present. Examples of such chromophoric systems containing cationic dyes are arylazo, Anthraquinones. Methine-, A "arn & thin- ··, Ariin-, 0>: &. Zin-, 'TbJazin-, Xanthene, acridine, polyaryl methane and coumarin dyes.

Fiber material pretreated according to the invention Polyacrylonitrile or polyacrylonitrile copolymers can be used if desired - using appropriate fiber-affine dyes - not only together with untreated Polyacrylonitrile fiber material, but also with other things

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untreated fiber material can be processed and dyed. For this purpose, fiber materials made from linear, high molecular weight esters of aromatic polycarboxylic acids are used polyfunctional alcohols, such as polyethylene glycol terephthalate fibers, and synthetic polyamide fiber material as well as the corresponding acid modified fibers in Consideration. For example, by dyeing fiber mixtures of pretreated polyacrylonitrile fibers, untreated Polyacrylonitrile fibers and unmodified polyester or synthetic polyamide fibers with a combination of the above-mentioned cationic dyes and customary disperse dyes are particularly interesting Achieve multicolor effects. The coloring of such fiber mixtures can also be done first with Dispersion and then dyed with cationic dyes. Such disperse dyes can be any Belong to dye classes; these are mainly azo dyes or anthraquinone, nitro, methine, Styryl, azastyryl, naphthoporinone, Cbinophthalone or Naphthoquinone imine dyes.

The pretreatment of the fiber material made of polyacrylonitrile or polyacrylonitrile copolymers with the optional Thickener-containing aqueous preparation of a cation-active compound according to the definition can according to the for dyeing or printing acrylonitrile fiber material

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customary methods take place, so for example by the so-called exhaust process in a long liquor (liquor ratio approx. 1:10 to 1:50), optionally under pressure, at temperatures between 85 ⁰ C and about HO ⁰ C, preferably 95 to 110 ⁰ C, during 30 to 180 minutes; by impregnation, particularly padding, for example in the form of slubbing, at temperatures below 80 ⁰ C, especially at 30 to 40 ⁰ C, and subsequent heat treatment, such as steaming, preferably with a 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 caulionic dye. Preferably, the coloring of aqueous becomes * liquor by the exhaust (liquor ratio of about 1:10 to 1:50) at temperatures of about 85 to 110 ⁰ C with the addition of customary dyeing auxiliaries, such as organic acids, especially acetic acid, for the purpose of a Fanstellung The pH of the liquor is between 3.5 and 5. The fiber material

2098 50/1 U 9

but can also be continuous, ie, colored by impregnating with a customary dyeing auxiliaries, such as color carrier and acid-containing thickened dye liquor and subsequent heat treatment, especially vapors at temperatures of about 98-105 ⁰ C.

"Depending on the type of pretreatment and combination of what is pretreated according to the invention with untreated, one obtains Fiber material made from polyacrylonitrile or polyacrylonitrile copolymers and optionally other untreated fiber material very effective two-tone and multi-tone effects. Fiber material pretreated according to the invention can can be stored anywhere and processed at any time and colored in the desired color tones, thereby reducing the costly There is no need to store large quantities of pre-colored material. The method according to the invention also makes it possible to use fiber material of the same quality in a simple way to dye in different shades, which is especially important for the Carpet production is of great importance because it would be able to produce carpets that are stable in terms of stability and the sheen of the pile show a balanced picture.

BATH

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Example 1

In a pretreatment bath containing 2.5 g Octadecylaniinäcetat, 2 ml 407 _o acetic acid and 1 g of sodium acetate dissolved in 1000 ml of water, 50 g of polyacrylonitrile (z. B. Orion 42) yarn introduced. The temperature of the liquor is increased to the boiling point within about 30 minutes with constant agitation of the textile material and then boiled for 90 minutes. The treated polyacrylonitrile yarn is then rinsed with warm water and then dried.

The 50 g of polyacrylonitrile yarn pretreated in this way are together with 50 g of untreated polyacrylonitrile yarn on a Knitting machine processed into a tricot.

The knitted fabric prepared in this way is then placed on a fresh bath which, in 2000 ml of water, contains 1.25 g of the dye of the formula

, S ~

-N = N

0-01)

N CH,

ZnCl

4 ml of AOZige acetic acid and 10 g of crystalline. ftatirluttsulfat contains :, colored for 60 minutes at boiling temperature; The dyed material is then 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: The one after the Above regulation has pretreated polyacrylonitrile yarn portion

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BAD ORJGJNAL

_O was added 87 of a total of unabsorbed dye, · on the unbchandelten polyacrylonitrile proportion accounted 92% of the unabsorbed dye.

If you replace the 2.5g octadecylamine acetate in the above example by the amounts given in the second column of Table I below of those listed in the third column Pretreatment agent and performs both the pretreatment as well as the dyeing in compliance with the conditions described in Example 1, similar light blue / dark blue effects are obtained on the knitted fabric. Those of the pretreated and Dye fractions taken up by untreated fibers emerge from columns 4 and 5.

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Table I.

at lot Pretreatment agent 3 SO ₁ CH X + x + x + X ₁ ^ 20 - ι f
H ' - 2 2 y CH ₊ Cl 2 y aufi.-t? n: .r.Ker.er Farbetcff in; ί ■ uricf; hir; dsltes game in g ^ 3 1234 I. CH COO CH, voi 'treated Polyacrylic No. C H - /}
17 33 \ k ^ CH CH OH 3 CH -Ii ^> \
0 Polyacrylic - nitr_.lr?.rn 1.5 C _Q H t _t f \ 1 Cl -
18 37 \ = z / J 12 25 y \ CH niti'il yarn 2 CH T +++ CH * 3 118 37
CH - K - (CH CH 0) H
PtT T 2.5 l / ti J.
', ² 2 80 3 20th ■ 2 CH - N - (CK CH 0) H 3 1 2 2 x CH 2 I 2 CH i 2 - "(CIi CH 0) H CH - N; "2 2 X ^ ^ (CH CH 0) H.
2 2 X ₁ 2.5 86 H 2.5 5 δ

BATH ORIGINAL

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Example 6

1 kg of polyacrylonitrile flakes (Orlon'42) are placed in a dyeing machine. Separately, a fleet is prepared, which in 15 l of water 30 g of octadecylpyridinium chloride, 40 ml Contains 40% acetic acid and 20 g sodium acetate dissolved. This pretreatment liquor is now pumped into the dyeing machine. The temperature of the liquor is then increased to the boiling point within 20 minutes and then boiled during 90 minutes. Then the pretreated polyacrylonitrile rinsed flake with warm water, spun off, dried and then spun into carpet yarn. The thus obtained, Carpet yarn with a weak affinity for cationic dyes is now used together with 1 kg of untreated polyacrylonitrile yarn of the same quality on a tufting machine to make a carpet processed. .

A piece of this carpet weighing 1 kg is now pulled into a reel runner and sewn at the ends. One lets now run in to the dyed material 30 1 of water at 40 ° and sets 100 g of crystalline. Sodium sulfate too. Has been separated in. 4 1 Water containing 40 ml of 40% acetic acid, 10 g of the dye of the formula

CH

Tj J V- N = N - N- (/ ^ -NO ₂ (102) ^^ N

CH ₃

. BATH ORIGINAL

7 λ ^ P ■ - Ρ « ■? 11 /. ©

2 g of the dye of the formula

(103)

CH ₀

- CH ^

SO ₄ CH ₃

(104)

and 1.5 g of the dye of the formula

CH ₃ O

CH

ZnCl

solved. The dye solution obtained is then cautious added to the dye liquor. The temperature of the liquor is then increased to 95 ° in the course of 45 minutes and then dyed during 60 minutes with a gentle boil. The colored carpet is then first washed with warm and then with cold water rinsed and dried. In this way, a carpet with a light brown and dark brown pattern is obtained.

The following color distribution was determined on the basis of reflection measurements; On the pretreated polyacrylonitrile yarn · share hiiVen 1 \% of. All in all, grown on enormous amounts of dye; the untreated polyacrylonitrile yarn portion accounts for 967o of the total absorbed dye.

Similar effects are obtained if, with otherwise the same procedure, instead of Orion 42 flake, polyacrylonitrile flake is used from Acrilan, Crilenka, Dralon or Exlan

BATH ORIGINAL

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Example 7

If the 30 g of octadecylpyridinium chloride in the preceding example 6 are replaced by 50 g of the pretreatment agent according to example 3, the pretreatment is otherwise carried out as described in example 6 and the carpet obtained by processing the treated and untreated fiber material is dyed under the conditions specified in example 6, however, instead of the dye combination given in the previous example, a dye mixture consisting of

6 g of the dye of the formula CHo

(105)

CLL

-N = N
CH

ZnCl.

(106)

and 6 g of the dye of the formula

= N

ZnCl.

is used, so erbä]. L one a light green / dark green colored carpet. The reflectance measurements showed the following values: In the pre-treated fiber fraction accounts for 19% ₅ on the untreated fraction 81% of the total of absorbed dye.

BATH ORIGINAL.

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Example 8

In Example 6, instead of the 30 g of octadecylpyridiniuin chloride 50 g of the pretreatment agent of the formula

(107)

12 25,

Cl

a, carries out the pretreatment as indicated in Example 6 and then dyes that which has been processed into a carpet in the same way Polyacrylonitrile fiber material in compliance with the dyeing conditions described in Example 6 with a Fai "bstoff mix, consisting of

4 g of the dye of the formula

(108)

- N

—Ff

Cl

and 8 g of the dye of the formula

(109)

ClI.

CH ₃

CIL

CH ₃ SO ₄

so you get a carpet, which

a) made of intensely scarlet colored untreated polyacrylonitrile yarn and

b) made of pretreated polyacrylonitrile yarn dyed slightly yellowish red

BATH ORIGINAL

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composed. The relationship between the treated and the untreated Polyacrylonitrile fiber material incorporated dye is 20:80.

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Example 9

If the pretreatment of the polyacrylonitrile flakes is carried out as in Example 6 described, but using 50 g of the quaternization product of N-dodecyl ~ N, N-dimethylamine with Epichlorohydrin instead of the 50 g used in Example 6 Octadecylpj ^ ridiniurnchlorid carried out and then in Fiber material processed into a carpet in the same way, consisting of equal parts pre-treated and untreated Polyacrylonitrile yarn in compliance with the dyeing conditions described in Example 6 with 5 g of the dye of the formula

(HO)

ZnCL

when dyed, a patterned carpet is obtained, made of a) made of intensely yellow-dyed untreated polyacrylonitrile yarn and b) from pale yellow colored pretreated polyacrylonitrile to s amme sets.

The lex ran ion sri: cs solution gives fclgcude FarbvcrLcilunf: On the front of treated polyacrylonitrile-share have grown 97 _O of the overall recorded Farbstoffinenge, · on the untreated portion accounts for 91% of the total dye.

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BATH ORIGINAL

Example 10

A printing paste containing 50 g / l of the pretreatment agent of the formula

(111)

Cl

5 g / l locust bean gum thickener and 5 ml / l 80% acetic acid, is made on a fabric with the help of a roller printing machine made of polyacrylonitrile fibers. The fleet order is. . 100% printing paste, based on dry weight of the fabric.

The fabric printed with this pretreatment agent is then treated for 15 minutes at a temperature of 120.degree and 1 Atü steamed, 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 e5.ne reel runner and sewn at the ends. Now you let 35 liters of water into the reel skid from -. 40 ° and sets 100 g of crystalline. Sodium sulfate too.

3 1 Was & er are made separately with 40 ml of 40X5g acetic acid added, whereupon 10 g of the dye of the formula.

° 2 ^N ~ \ / - ^{N = N} --V- /

Cl

Cl

admits. The dye solution prepared in this way is now carefully added to the liquor. Then, the temperature of the dyebath is increased within 50 minutes to ¹ 95-97 C. Then color

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ORIGINAL BATHROOM

one for an hour with a gentle boil. One receives on In this way, a color print in which the areas printed with the pretreatment agent are pale red and the areas not printed Places, on the other hand, are colored intensely red.

In this example, if the 50 g pretreatment agent of the formula is replaced

(113)

egg ©

by the same amount of one of the pretreatment agents listed in Table II below in the second column and applies to both the pre-treatment and the subsequent treatment Coloring as described in Example 10, color prints with a pale red / intense red pattern are also obtained.

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BAD ORiGINAL

Table II example

No.

Treatment medium; eel

CH - ^{12 25}

CH ² 5

CH CK OH 2 2 -J

Cl

CH -N ¹

.CH CH OH / 22

CH CK OH

2 2. -J

-H Br

C "H 18 37

-10

-H HCCO

CH

CH -CH-O (CH CH 0) H ^X l

_o H _Γ -Η

CH -CH-O (CH CH, 0} H CH ^X 2

H Cl

X + x = 1-0 1 2

fCH CH 0) H ^{2 2} \

^ ^N CH CH-O (CH CH 0) H CH 21 2 2 x

3 J ^

χ + x = 10 1 2

CH « ^{18 35} j ^

CII CH CH ^{2 2}

jCH CH CH j 2 2

CH -CH -OCH 2 2 3

Br

c H co:; h (ck) -Fi ^{11 2} > ²³ I.

/ CH

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Continuation of table II

example
No. Pretreatment agent, - H Cl Cl C "H -OCH -K 7
18 35 2 \ = V
CH Cl H - ■
Cl 18th OCHCHCHN (Ch) I ⁺ CHSO-
Yy yy _y ? .N- CH
CH -C ^ I ²
17 35 \ '
^N N - CH ₂
CH CH 0 «
2 2 -H Br 19th CH CONH (CH} H -
17 33 ^{2 2} ^ c V
2 * 5- , N-CK
CH - / IJ-
^{1323 X} N-CH
I 2
CH
3 H . Cl 20th C _O H -II V
18 37 \ zlJ
CH , N - CH -
■ a? 2 ^
CH-C CH
17 33/2 21st • ^ ^N - f ₂ "
CH-C I - 22nd 23 24 25th

209850/1149

Continuation of table II

example
No. • Pretreatment agent 1 CH ₅ ⁺ CH • + / KH + 3 x ¹ ^ - + Cl • Cl -ι + CH SO "' Cl + _χ Ν - CH CH ^ N-CH
³ \ hc ^. Il - II CH - c '
^{11 2} ^ N _NH . CH ₂ _ • - H Cl CH - C ^{- /} - j CH ^ . ^ H- CH
3 ι CH - C
I ₇ 35 \ / CH _
M. -f-
CH SO
- H 3 4 28 O ~ f ^H 2 'I.
C, H
16 33 IJ
^ CH - 26th CH - C ^ CH
³ \ / ² y NH N -CH ₂
CH
12 25 CH -C ^ ^ N-CH ». Clf | i ^ N - CH
I. 1
CH
12 25 ^30th 32

209850 / 1U9

Portion of Table II

example

No.

Pretreatment agent

CH - C ^ ^{17 35} ^

NH

NH (CH) OCH H Cl

CH 3

CH, 3

C ₁ H -N - CH CH -K- CH 14 29 j ²² I.

CH CH

3

CH CH OH ι 2

CH - N - CH CH CH - H

¹⁷³⁵ I ^{2 2 2} I ^

CH CH

.CH CH OH S 2

HCH 2 2 cl

(CH CH 0) H (CH CH 0) H j 2 2 X ₁ I 2 2 X ₂

CH - N - CH CH - N - CH CH - N 17 35 2 2 2

x + x + x + x = 15 12 3 CH CH 0 H

H 3 Cl

NH "ι +

^ N-CH

C 'H -NH-C ^ l6 33 \

^N HH - CH CH OH 2 2 -J

H Cl

N - CH C ₈ H - NH - C '\

NH-CH

H CH COO

209850/1149

Continuation from Table II

example
Mr. ". Pretreatment Agents +
- · H Cl "■ +
-H
Br + HO MH ~
CH - S - C ^ -
12 25 \
^X KH
2 , KH
<r -
CH - S - C. . +
H Cl do
* HH
^c i2 ^H 25 - ^s - \ r \ -
^x kh- (h> HZ ^, CH
' 3
CH -S-
12 25 ν
^ CH CH OH
2 2 - ¹

209850/1149

Is used in Example 1 instead of 2.5 g of octadecylamine acetate the same amount of the pretreatment agents given in the preceding Examples 10 to 43, results in the Pretreatment as described in Example 1 and then dyes the knitted fabric produced in an analogous manner if the conditions given in Example 1 are observed, knitted fabrics are obtained which have a similarly good light blue / dark blue two-tone effect.

209850 / 1U9

Example 44

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

(114)

2 ml of 40% acetic acid and 1 g of sodium acetate in 1200 ml of water contains dissolved, 50 g of polyacrylonitrile yarn are introduced. 'With constant movement of the textile material you now increase the The liquor temperature rises to 95 ° over the course of 30 minutes and then boils for 90 minutes. The treated polyacrylonitrile yarn is then rinsed with warm water and dried.

50 g of untreated polyacrylonitrile yarn are now put together with the polyacrylonitrile yarn pretreated in the manner described above processed into a tricot on a knitting machine.

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

(115)

N - N-

Cl

CH ₂ CH ₂ N (CH ₃ ).

NHn

4 ml of acetic acid containing dissolved 407 ₀ ig and 10 g of sodium sulfate, the knitted fabric for 60 minutes will now be dyed at the boil. The material to be dyed is then rinsed with warm and then with cold water and finally dried.

In this way, a knitted fabric is obtained which shows a slightly yellow-brown / intensely yellow-brown two-tone effect.

209850/1 149

BAD ORlGiNAL

The following color distribution was determined by reflection measurements

the
provided: The polyacrylonitrile yarn portion pretreated in / described has absorbed 9% of the total absorbed dye! the untreated portion accounts for 91% of the total absorbed dye.

If polyacrylonitrile yarn is used according to the information in the example 44 pretreated and processed with untreated polyacrylonitrile yarn, and is used to dye the knitted fabric instead of the 0.5 g of the dye indicated in the preceding example 44, 1 g of one of the dyes in column 2 of the following If the dyes listed in Table HI are used, colored shades are obtained in the colors indicated in columns 3 and 4 ■ Knitwear.

209850/1149

Table III

example
Mr.

Dye shade on polyacrylonitrile yarn

treatment

C H

\ _

Cl

weak
bluish tint
Red

intense bluestior.ig Red

C H

\ -,

weak
yellow-brown

Cl

intense yellow-brown

HH-CH

NK (CH) N (CH)

CH SO ₁ 3 4

weak
blue

intense blue

-μ

_H 2 5

ZnCl

weak
pink

intense red

CH

CH

CH SO 3 4

weak

intense yellow

egg

_{c H}

²

Cl light brown

Cl

CH HK 13

H C

CH

3 SH

Cl.

Cl light blue

dark brown

intensive

blue

20eiSQ / 1U

BATH ORIGINAL Example 52

Ground 300 g polyacrylonitrile in a closed laboratory swab yarn introduced in the form of a package. A pretreatment liquor is separated, which in 4.5 l of water 30 g of the pre-treatment agent of the formula

C ₁₇ H ₃₃ COKH (CH ₂ ) ₃ N (CH ₃ ) ₂ H Cl

(116)

Contains 12 ml of 40% acetic acid and 6 g of sodium acetate. This pretreatment liquor is now allowed to run into the dyeing apparatus, the temperature is increased to ^{105-107 ° C.} within 45 minutes and this temperature is maintained for 90 minutes. Finally, it is cooled to room temperature, the material to be dyed is rinsed with warm water, spun off and then dried.

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

The knitted piece made in this way is now placed in a reel runner moved in. 40 l of water are then run in and 80 g of an emulsion of the sodium salt are used as swelling agent ο-phenylphenol and 80 g of diammonium sulfate. Under constant Moving the textile material increases the temperature of the dyebath within 15 minutes. 60 ° G.

209850/1 U9

BAD ORJGiNAL

Separately, in approx. 500 ml of water, 2 6 g of a dye f .......

preparation, which contains the dye of the formula

(117) CHoO - V ^x > - N = N - CH ⁰ V = / ^x

NO

CO

Cl

CO -

* contains in finely divided form, slurried. The dye dispersion obtained is now carefully added to the dye liquor, whereupon the temperature of the liquor is increased from 60 to 95 ° within - 30 minutes. It is then dyed for 90 minutes with gentle boiling .. The material to be dyed is then rinsed with hot water, then soaped and rinsed again with water.

The overdyeing of the treated and the untreated polyacrylonitrile yarn portion is then carried out as follows :

The mixture is left in the winch again 40 1 of water at 40 ⁰ C is run in and 100 g cryst. Sodium sulfate too. Separated in 5 liters of water, which contain 32 ml of 40% acetic acid, 10 g of the dye of the formula

(118)

Cl

solved. The dye solution obtained is then carefully added to the dye liquor. Thereafter increasing the temperature of the liquor within 1 hour at 95 ⁰ C and then stained during

209850 / 1U9

60 minutes with a gentle boil, after which you knit the piece Rinse with warm water, spin dry and finally dry. If the above conditions are observed, a knitting piece, which

a) made of greenish yellow colored polyethylene glycol terephthalate yarn,

b) made of light green colored pretreated polyacrylonitrile yarn and

c) made of an intensely bluish green colored untreated polyacrylonitrile yarn composed.

20 9850/1 U9

Claims (17)

Claims 1. A method for producing multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copolymers, characterized in that fiber material made of polyacrylonitrile or polyacrylonitrile copolymers with an aqueous preparation, optionally containing thickener, of an uncolored, cation-active organic ammonium or sulfonium compound having at least one higher alkyl radical at temperatures of at least 85 ^° C. and a pH value between 3 and 5 and at least one fiber material pretreated in this way dyes with at least one cationic dye together with untreated fiber material made of polyacrylonitrile or polyacrylonitrile copolymers. 2. The method according to claim 1, characterized in that it is pretreated with an aqueous preparation, which is a cationic organic ammonium compound contains, which is an alkyl radical having 8 to 22 carbon atoms and whose cationic part of the molecule carries only a single positive charge. 3. The method according to claim 2, characterized in that that one pretreated with an aqueous preparation, which as a cationic organic ammonium compound, 20 98 50/1 U9 at least one compound of the formula R - (CO - NH - (CH ₂ ) _n ) _r _ ₁ - R ¹ R ° - C or R - (Q) _8-1 - , Vl 'NO vr ι viii contains where R is an alkyl radical with 8 to 18 carbon atoms, R 'and R "are each hydrogen, optionally by'Hydroxyl, lower alkoxy or cyano-substituted lower alkyl, cycloalkyl or a polyalkylene glycol radical or R ^? and R "together with the nitrogen atom connecting them a piperidine or morpholine ring, R "'is hydrogen, lower alkyl or aralkyl which is optionally substituted by hydroxyl or lower alkoxy, or R ', R "and R ¹ " together with the nitrogen atom connecting them form a pyridine ring which is optionally substituted by lower alkyl,. one of the radicals R °, R ^1V and R ^{v is} an alkyl radical having 8 to 18 carbon atoms and the other is hydrogen, optionally alkyl substituted by hydroxyl or 209860 / 11-49 BATH ORIGINAL Aralkyl,
Z is a saturated or unsaturated alkylene radical 2 or 3 carbon atoms,
R, R and R each hydrogen, optionally lower substituted by hydroxyl or lower alkoxy Alkyl, cycloalkyl or aralkyl, Q sulfur or -NH-,
r and s each l'or 2,
η 2 or 3 and X mean the anion of an organic or inorganic acid. 4. The method according to claim 3, characterized in that it is pretreated with an aqueous preparation, which as a cationic organic ammonium compound is at least one compound of the formula R- (CO-NH- (CH ₉ )) ->% - R " contains, wherein R, R ¹ , R ", R"', n, r and X have the meaning given in claim 3. 5. The method according to claim 4, characterized in that pretreated with an aqueous preparation, which as cation-active organic ammonium compound a compound the formula 209850/1149 R ¹ " contains, wherein R, R ¹ , R ", R ¹ " and X have the meaning given in claim 3. 6. The method according to claim 5, characterized in that there is a cationic Atnmoniumver compound of the formula eat ^R i - used where R-, an unsubstituted alkyl group with 8 to 18 carbon atoms, R «and R independently of one another each hydrogen, one optionally by hydroxyl, lower alkoxy or
Cyano-substituted lower alkyl radical, a cycloalkyl radical or a polyglycol ether chain with 2
up to 40 alkyleneoxy groups, or R “and Ro together with the nitrogen atom connecting them a piperidine or morpholine ring, R, hydrogen, a lower alkyl radical which is optionally substituted by hydroxyl or lower alkoxy groups or an aralkyl radical and X represent the anion of an organic or inorganic acid. 209850/1149 7. The method according to claim 3, characterized in that as cation-active Atnmo niumver connection compounds of the formula K ₅ - co ... _{(ay B} ^ used where R, hydrogen, a lower alkyl radical which is optionally substituted by hydroxyl or lower alkoxy groups or an aralkyl radical, R ₁ - an unsubstituted alkyl group with 11 to 17 carbon atoms, R _fi and R-, each an unsubstituted lower alkyl group, η 2 or 3 and X is the anion of an organic or inorganic acid. 8. The method according to claim 3, characterized in that compounds are used as the cation-active ataraonium compound the formula "- R used where Ro a possibly interrupted by oxygen atoms, unsubstituted alkyl chain with 8 to 209850/1 1 Carbon atoms, R _{Q is} hydrogen, the methyl or ethyl group and X is the anion of an organic or inorganic acid. 9. The method according to claim 3, characterized in that the cation-active ammonium compound is compounds the formula C-R 11 or R ,, not hydrogen used where of R, _Q and R ,, one R is an unsubstituted alkyl group with 11 to 18 carbon atoms and the other R is hydrogen or a lower alkyl radical optionally substituted by hydroxyl groups, R, 2 hydrogen and - if R ₁ mean - also a lower alkyl radical optionally substituted by hydroxyl groups or for one Aralkyl radical, η 2 'or 3 and X mean the anion of an organic or inorganic acid. 10. The method according to claim 3, characterized in that 209850/1 U9 that one as a cationic ammonium compound compounds the formula CH -γ C-R 14th CH - used where R, ο an unsubstituted alkyl group with 12 to 18 carbon atoms, R ,, hydrogen, an unsubstituted alkyl group with up to 18 carbon atoms or the unsubstituted Phenyl radical, R, c is an unsubstituted lower alkyl group or den Benzyl radical and X is the anion of hydrochloric or hydrobromic acid or of methylsulfuric acid mean. 11. The method according to claim 3, characterized in that the cation-active ammonium compound is compounds the formula sfc® - Ri - C ^X N - R, ^R 16
used where "5 18th
17th 209850/1 U9 Rc is an unsubstituted alkyl group with 11 to 17 carbon atoms, R ,, -, R, η and R-jo each independently of one another hydrogen, a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, a cycloalkyl or aralkyl group and X is the anion of an organic or inorganic acid mean. 12. The method according to claim 1, characterized in that the cation-active ammonium compound is compounds the formula R-. , 19th N - N - R ₁₉ R / used where R, ο one which is optionally substituted by hydroxyl groups lower. Alkyl radical, especially the methyl radical: or a polyglycol ether chain with 2 to 40 alkyleneoxy groups or phenylethyleneoxy groups, η 2 or 3 and m is an integer from 1 to 4, and R ,, R, and X have the meaning given in claim 5. 209850/1149 13. The method according to claim 3, characterized in that that the cation-active ammonium compound is compounds of the formula - ^R R ₁ - NH - 21st - H used where R, an unsubstituted alkyl group of 8 to 18, preferably 12 to 18 carbon atoms and R2 ₀ and R ₂ -] independently of one another each represent hydrogen or a lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, where R " _o and Rp, together with the group Can form a ring and
X has the meaning given in claim 3. ™ also includes the rest of a partially saturated 14. The method according to claim 3, characterized in that the cation-active ammonium compound is compounds of the formula> ._. _ ^ N - R, R ₁ -S- 22nd yß used where R, an unsubstituted alkyl group of 8 to 13, preferably 12 to 18 carbon atoms and 209850/1 U9 Rpr ,, Roo and R ~, each independently hydrogen, one lower alkyl radical optionally substituted by hydroxyl or lower alkoxy groups, a cycloalkyl or aralkyl radical, especially the cyclohexyl or benzyl radical, mean, where R "P and R" o together with the group -C ^ _n also the remainder ι a partially saturated ring, can form and X has the meaning given in claim 3. 15. The method according to claim 1, characterized in that the cation-active sulfonium compound is compounds of the formula ^R x - used where R, an unsubstituted alkyl group with 8 to 18 carbon atoms and R _{? R} and R ^ ς each represent a lower alkyl radical which is optionally substituted by hydroxyl groups. 16. Use of the cationic ammonium and sulfonium compounds according to one of claims 1 to 15 for the production of multi-tone effects on fiber materials made of polyacrylonitrile and polyacrylonitrile copolymers. 209850/1 U9 17. The according to claims 1 to 15 in different Shades of colored fiber material made of polyacrylonitrile or polyacrylonitrile copolymers. FO 3.31 / Ro / pm
31.3.1971 '- 2if11 CJi O ££ Γι / * ίΙ * $ β US ό BU / Ι 14