DD202466A5 - METHOD FOR INFECTING FIBERGY OF ACRYLONITRILE POLYMERIZATED FROM ORGANIC SOLVENTS IN RELIABLE CONDITION - Google Patents

Abstract

After a wet spinning process, not dried fiber material of still swollen texture (gel form) of acid-modified homo- or copolymers of acrylonitrile (PAC fiber) can be advantageous and colorfast with soluble dyes faerben, which in their molecule more compared to the acid groups of Fiber substance basic groups, namely have more than one quaternary grouping and / or uncharged, strongly basic grouping. The chromophore of this colorant may be from the category of monoazo or diazo dyes, methine, azamethine or diazamethine dyes or naphtalactam dyes. The dyeing of the wetted spun material is carried out according to the invention continuously or discontinuously from a solvent-containing dye bath which, in addition to water, also has fractions of an organic solvent, especially that used for spinning the polymer; the stretching of the fibers can be done before the dye application, during the dyeing process itself or immediately thereafter.

Description

The present invention relates to dyeing in the course of the production process of produced by a conventional Uaßspinnverfahren fiber material, such as slivers or filaments of acid-iaodifi ornamental th polymers or copolymers of acrylonitrile, in the gel state and optionally before the final Vers'tr cornering, with solutions of towards the acidic groups of the fiber substance basic behaving dyes, which in addition to water still contain a higher content of an organic solvent - especially of the solvent used for spinning the polymer -

Characteristic of the known technical solutions

Various processes for the production of continuously dyed, wet-spun acrylic fibers are already described in the context of the spinning and drawing process. For example, wet-spun acrylic threads are dyed after washing, before or after drawing, while they are still in the swollen, undried state (FR U.S. Patent No. 4,995,700; Japanese Patent Publication No. 24,495; U.S. Patent No. 3,113,827). Other publications (CS-PS 104 915, U.S. Patent No. 3,111,357, British Patent No. 3,991,957) disclose the dyeing of wet-spun acrylic filaments during the stretching operation , the higher the draw is, the higher the dye uptake is. Particularly fast dyeings of wet-spun acrylic fibers can be achieved if the dye is added directly to the coagulation bath, because then the dye can immediately penetrate into the forming fiber whose structure is still loose (US Pat. No. 3,242,243 and CS-PS 95) 939) · This immediate

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Spinning of acrylic fibers into a dyebath is known in the art as "Neochrome Staining" (Man-Made-Textiles, August 1966, pages 58).

However, a major problem with such a continuous gel dyeing is the maintenance of the dye concentration during the dyeing process. Due to the moisture content of the slivers or filaments namely water is constantly introduced into the fleet and thus reduces the concentration of the dye solution accordingly. As a result, unevenness in the appearance of the color produced in this way caused.

Another difficulty in dyeing wet-spun Acrvl fibers in the gel state is the achievement of good fastness properties. In the case of the presence of relatively high proportions of solvents or spinning bath liquid in the spinning material, the use of conventional basic dyes causes rapid and sometimes deep dyeings by diffusion processes, but in this way dyed fibers and threads tend to be used in subsequent fabrication processes, for example in steaming, washing , Equip and also while stretching to bleed heavily.

However, this finding means a loss of color strength for the polymer to be dyed and, moreover, also a color run-off if, at the beginning of a dyeing, dyestuff-free stretching, washing and bathing baths containing cationic or anionic softening agents are still present. Under the given conditions, these baths have the tendency to be charged with dyestuff during the further production process. "In addition, the use of hitherto usual, strongly bleeding dyestuffs results in a not inconsiderable amount of

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pollution, which is particularly annoying if the staining operation is changed to another nuance.

The gel-dyeing of threads of acrylonitrile polymers in the aqueous medium, however, represents a complicated process for which a special dye selection is required. According to DE-OS 2,043,090, it has also been attempted to carry out the dyeings themselves from a pure organic solvent or a mixture of several organic solvents and the gel-wet fiber with dissolved in these solvents dyes at temperatures below the boiling point of the dyeing medium treated. However, the results of staining were unsatisfactory.

It is known in all dyeing processes on the basis mentioned above, the use of basic dyes containing only a single quaternary group or only a single aliphatic bound, primary, secondary or tertiary amino, guanidino or hydrazino group. If, of course, such basic dyestuffs are used for dyeing the gelled polymers in the gel state from dye baths which contain, in addition to water, even larger amounts of an organic solvent, especially of the solvent used for spinning the polymer, then one observes only a moderate dye uptake or Fixing by the Polymer Compared to Dyeing from a Pure Aqueous Bath · The higher the content of the organic solvent in the liquor, the lower the dyeing off and the lower the fastness to washing of these dyeings.

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Object of the invention

The aim of the present invention is now to eliminate the problems identified in connection with the gel dyeing, to eliminate the described deficiency and to improve the resulting according to the previous dyeings, but not sufficient fixation properties.

Explanation of the essence of the invention

This problem is solved according to the invention by using for the gel dyeing of the acrylic fibers defined in more detail below those dyes which have in their molecule more than one group which has a basic behavior relative to the acidic groups of the fiber substance.

These recognized useful dyes can be used in the claimed process both as individual dyes as well as for combination dyeings · They are characterized by a rapid and strong fixation in the polymer, so that the disadvantages associated with the conventional method of operation can no longer occur »It also arises within evenly dyed threads from short dyeing times over the entire fiber cross section.

The above-mentioned groups considered to be characteristic features of the present invention can be the same or different from each other. Such groups, which behave basicly with respect to the acidic groups of the fiber substance in the molecule of the selected dyes, are more than one quaterary group, or a quaternary group and additionally one

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or more than one aliphatically bound, primary, secondary or tertiary amino, guanidino, amidino or hydrazino group,

Such basic dyes found suitable by the practice of quaternary groups in the molecule according to the method embody compounds of salt-like construction and consist of dye cation F, which is the chromophoric component and that compared to the dye anion Σ, which is mainly responsible for the solubility of the product responsible for the relatively larger portion of the molecule (higher cation weight).

Suitable quaternary groups for basic dyes of this type are, for example, ammonium groups, such as, for example, a trialkylammonium group with lower alkyl radicals which may optionally be substituted, furthermore a WjN-dialkyl-1-aryl-ammonium group with optionally substituted lower alkyl radicals; , H-dialkyl-1-aralkyl-ammonium group having lower, optionally substituted alkyl groups, and a U-monoalkyl-N-aryl-IT aralkyl-ammonium group having a lower, optionally substituted alkyl group; these ammonium groups are bonded either directly or via an optionally heteroatoms and / or small organic moieties as a bridge member having aliphatic radical to the aromatic part of the chromophoric system, such as a benzene or Uaphthalinkern; if in these ammonium groups several substituents from the

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same category are present on the same nitrogen atom, they may be both identical and different from each other.

Quaternary groups of the dyes which can be used according to the invention are furthermore lower dialkylhydrazonium groups and cyclammonium radicals, preferably of an aromatic character, in particular mesomeric 5- or 6-membered, positively charged rings which may contain further heteroatoms, such as oxygen, sulfur and / or nitrogen atoms.

These cyclammonium radicals may be part of the chromophoric system or may be directly attached to or fused to an aromatic carbocyclic radical, such as a benzene nucleus or naphthalene nucleus. Cyclammonium radicals and derivatives thereof are, for example, pyridinium, pyrazolium, imidazolium, triazolium j tetrazolium, oxazolium, thiazolium, isothiazolium, oxdiazolium, thiadiazolium, isothiadiazolium, quinolinium, indazolium, benzimidazolium, bentriazolium, benzisothiazolium, benzthiazolium, arylguanazolium or benzoxazolium radicals, these radicals being in the heterocycles may preferably be substituted by lower, optionally substituted alkyl radicals, by aralkyl, aryl and / or cycloalkyl radicals and in the aromatic carbocyclic moieties by quaternary, such as those mentioned above, by other basic and / or non-substituted ionogenic groups may be substituted; such basic groups (without quaternary charge) are, for example, primary, secondary or tertiary amino groups, hydrazino, guanidino or amidino groups, furthermore heterocyclic, nitrogen-containing rings, for example the pyridine, imidazole, morpholine, piperidine or piperazine ring and non-ionic groups are, for example, halogen atoms, such as chlorine or bromine atoms, lower, lower

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optionally substituted alkyl groups, lower alkoxy groups, the hitro group, the sulfamoyl or carbamoyl group, a lower alkyl, phenyl and / or benzyl substituted sulfamoyl or carbamoyl group, lower carbalkoxy, lower alkylsulfone and lower alkanoylamino, the benzoylamino group, the trifluoromethyl and cyano group.

In the above as in the following mean: The statement "low" that the alkyl, alkylene or alkoxy radical characterized in more detail by this specification consists of 1-4 C atoms;

the term "substituted alkyl" means that the alkyl is substituted by one or two, preferably one, substituent selected from hydroxy, acetyloxy, lower alkoxy, cyano, lower carbalkoxy, such as carbomethoxy and carboethoxy, chloro, phenyl and carbamoyl Phenyl itself may be substituted by halogen, such as chlorine, bromine or fluorine, lower alkyl, lower alkoxy, iJitro, acetylamino, sulfamoyl and / or carbamoyl and the carbamoyl in turn by lower alkyl, a phenyl or a benzyl radical mono- or Thus, an alkyl radical substituted in this sense is, for example, a β-hydroxyethyl, β-cyanoethyl, β-acetoxyethyl, hydroxypropyl, β-methoxyethyl, benzyl or phenethyl group; the term "aryl" is an aryl radical, in particular a phenyl or naphthyl radical, which may be substituted by the abovementioned quaternary, basic or non-ionic groups; Non-ionic substituents, of which preferably 1 to 3 may be contained in the aryl radical, are in particular halogen, such as chlorine or bromine, lower alkyl, such as methyl or ethyl,

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lower alkoxy such as methoxy, ethoxy or propoxy, nitro, lower alkylsulfone and trifluoromethyl; the term "aralkyl" is a lower alkyl radical which is substituted by an aryl radical, the aryl radical having the abovementioned meaning; the aryl radical in the "aralkyl" is preferably a phenyl radical which may be substituted by 1 or 2 substituents from the group consisting of lower alkyl, lower alkoxy and chlorine;

the term "cycloalkyl" is a cycloalkyl radical of 4 to 12 ring C atoms, such as the cyclopentyl or cyclohexyl radical, which may be substituted by 1 to 3 lower alkyl groups, such as methyl groups. "

lower alkyl groups (alkyl radicals) are, in particular, the methyl and ethyl groups, lower alkoxy groups, in particular the methoxy and ethoxy groups, aralkyl radicals are in particular the benzyl and phenethyl group.

Preferred (quaternary) ammonium groups are the trimethylammonium group, the triethylammonium group, the dimethylethylammonium group, the benzyl-dimethyl-ammonium group and the phenyl-di-methyl-ammonium group.

lower, substituted alkyl radicals which are bonded to a nitrogen atom with the alkyl, are preferably alkyl groups of 1-4 C atoms which are substituted by a hydroxyl, lower alkoxy, cyano or phenyl group, for example the β-hydroxyethyl , ß-Cyanäthyl-, ß-Methoxyäthyl-, the benzyl or Phenäthylgruppe.

The basic quaternary dyes useful according to the present invention preferably contain, as the anion X.sup.11, the anion of a strong inorganic or .alpha

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organic acid such as sulfuric acid or its (lower alkyl) half ester (= lower alkosulfate), hydrochloric acid, phosphoric acid, perchloric acid, tetrafluoroboric acid, rhodanilic acid, acetic acid, chloroacetic acid, trichloroacetic acid, formic acid, oxalic acid, lactic acid, propionic acid or malonic acid. Furthermore, the dyes may be present as chlorides in the form of their double salts with zinc chloride. The nature of the anion is irrelevant to the coloristic properties of the dyes used according to the invention, insofar as they are colorless anions. At a low percentage by weight of the anion, dyeings having a particularly high tinting strength are obtained achieved. In addition, the anion should be selected so that the resulting Farbstoffsalz.wasserlöslich.

In particular, T ^ ~ 'represents the equivalent of the sulfate, phosphate, oxalate or tetrachlorozincate anion; or the chloride, bromide, tetrafluoroborate, rhodanide, acetate, monochloroacetate, trichloroacetate, trichlorozincate anion, or the lower alkyl group alkosulfate anion, such as the methosulfate or ethosulfate anion.

Among the dyes which can be used according to the invention, mention should be made of those quaternary dyes whose cationic charge is delocalized, which can be expressed in terms of form by various mesomeric boundary structures.

In particular, the claimed process is also advantageously advantageous with dyes which can be used according to the invention and which have one or more other strongly basic groups in addition to the quaternary group (s). Such strongly basic groups (without quaternary charge) are included

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For example, primary, secondary or tertiary amino groups which are bonded via an optionally heteroatoms and / or small organic moieties as a bridge member having aliphatic radical to the dye chromophore, further hydrazino, guanidino or amidino groups; the amino groups may also be part of a heterocyclic ring, such as the pyridine, imidazole, morpholine, piperidine or piperazine ring. Secondary amino groups are preferably lower monoalkylamino groups, aryl or aralkyl amino groups, such as, for example, the ethylamino, ethylamino or isopropylamino group or the phenylamino or p-methylphenylamino group. Tertiary amino groups are, for example, the dimethylamino, diathylamino, H-methyl-1-anilino, U-A * thy 1-anilino or H-methyl-1-benzylamino group.

Heteroatoms and smaller organic groups, which have just and previously been mentioned as a bridge member and via which the amino or ammonium groups may be bonded by means of aliphatic radicals to an aromatic ring of the dye molecule, are for example groups of the formulas -0-, -HH-, - !! (lower alkyl) -, -CO- or -SOp-; the aliphatic chains in turn are z. B. -CHp-, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH (OH) -CH ₂ -; and combinations of these with each other and with each other, as well as those that can be seen in the examples »

Dyes which themselves contain no quaternary group, but contain more than one strongly basic group (without quaternary charge) of the type described above, via an aliphatic intermediate (as above) attached to the dye chromophore, can likewise be used in the new dyeing process.

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The basic dyes used in accordance with the invention, which bind strongly and rapidly in the polymer, can belong to the most varied classes of dyes, in particular the class of the monoazo dyes, the disazo dyes, the methine, azamethine and diazamethine dyes and the lthalocyanate dyes. e ·

Of the basic monoazo dyes which can be used according to the invention, particular preference is given to dyes of the general formula (1)

D ⁽⁺⁾ - U = NK

or 2 X ^, if K contains a quaternary group, (1)

to name in which

D ^ ⁺ ^ is the radical of an aromatic carbo- or heterocyclic diazo component having one of the abovementioned quaternary groups, where D 1 'is in particular a pyrazolene, triazolium, - thiazolium, thiadiazolium, indazolium, benzotriazolium, benzimidazolium Represents benzthiazolium or benzisothiazolium radical and these cyclammonium groups and the optionally fused thereto aromatic carbocyclic radical, as described above, may be substituted, or D ^ ⁺ 'is an aromatic carbo- or heterocyclic radical having a directly attached to him or, as for example, mentioned above, with a via a bridge member to him bound (quaternary) ammonium group, in particular a trialkylammonium or Di alkylhydrazoniumgruppe, these aromatic radicals are in particular radicals of benzene, naphthalene and benzothiazole; K is the radical of an aromatic carbo- or heterocyclic

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Coupling component is, in particular from the benzene, naphthalene or indole series, preferably from the ΪΤ, ίί-dialkylaminobenzene and IT, U-dialkyl-aminonaphthalene, the IT-alkyl-U-aralkyl-aminobenzene and -naphthalin-, the ₍ N, U-bis (aralkyl) aminobenzene and naphthalene, the U-alkyl-U-arylaminobenzene and the U-alkylindole series, wherein the aromatic carbocyclic radicals of the coupling component K preferably by 1, 2 or 3 Substituents from the group lower alkanoylamino, benzoylamino, lower alkyl, lower alkoxy, Uitro, hydroxy, amino, lower alkylamino, lower dialkylamino, chlorine and trifluoromethyl may be substituted · This radical of the coupling component K in turn has at least one, to the aromatic nucleus directly or via a bridge member (such as mentioned above), aliphatically bonded primary, secondary or tertiary amino group 'or a (§uartäre) ammonium group, which may optionally be part of a 5- or 6-gliedri gen-aromatic heterocyclic ring (z. B. Cyclammoniumrestes), an amidine, guanidines, hydrazine or a Thiuroniumrestes can be; these basic radicals are preferably bonded via the alkyl radical of a lower IT-alkylamino group (bridge member) as a substituent on the aromatic nucleus of K, while optionally a second lower U-alkylamino group in the alkyl radical present there by chlorine, hydroxy, lower alkoxy, aryloxy, cyano, acylamino such as lower alkanoylamino or benzoylamino, or may be substituted by lower carbalkoxy;

and X.sup.1 '' as an equivalent of an anion has the meaning given above.

Of the basic monoazo dyes which can be used according to the invention, those of the general formulas (2a), (2b) and (2c) are also preferred.

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' (or -Q ₂ ) 13- .4.1932. C 231 756 AP D 06 P / ) of the X ^l ~ / '(or -Q ₂ ) 59 370/11 £ JL / or X ^ " (2a) D ^ ⁺ ) -N = N-Ar-NBQ ₁ ^ ^{+ L} R ) (2 B) D ^ -N = N-Ar-OBQ ₁ ^ ⁺

-ST = N-Ar-Ii

'B-Q.

(2c)

to name in which the individual formula radicals are defined as follows:

D ^ 'as indicated above; - '

D ₁ is the radical of an aromatic carbo- or heterocyclic diazo component, in particular of the benzene or naphthalene series, which may contain the abovementioned basic (without quaternary charge) and / or non-ionic substituents, where D _{1 is} preferably the phenyl or naphthalene radical substituted by 1-3 substituents from the group lower alkyl, lower alkoxy, Pluor, chlorine, bromine, lower alkanoylamino, benzoylamino, nitro, cyano, lower alkylsulfone, phenylsulfone, trifluoromethyl, carbamoyl, sulfamoyl, by lower alkyl, phenyl and / or Benzyl-substituted carbamoyl or sulfamoyl, and lower carbalkoxy may be substituted;

Ar is a p-phenylene or 1,4-naphthylene radical represented by 1 or 2 substituents from the group lower alkyl, such as methyl or ethyl, lower alkoxy, such as. Methoxy or ethoxy, halogen, such as chlorine or bromine, nitro, lower alkanoylamino, such as acetylamino, and trifluoromethyl substituted

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can be;

R is a hydrogen atom or a lower, optionally substituted alkyl radical, an aralkyl or cycloalkyl radical; B represents a divalent aliphatic bridge member, in particular an alkylene radical of 1-6 C atoms, preferably of 2-4 C atoms, mainly, the ethylene or propylene radical, or a lower alkylidene radical, such as the vinyl radical, such an alkylene B may in turn be substituted or attached via smaller organic moieties, such as -CO-, -O-C0-, phenoxy or -SOp-, to the nitrogen atom of the arylamino group or to Q ₁ or " ¹ Q ^;

Q ₁ is a (quaternary) ammonium group, in particular a lower Trialky! Ammonium, lower ΪΓ, υ-dialkyl-lJ-aralkylammonium, lower dialkyl hydrazonium group or .ein Cyclammoniumrest, in particular from this a pyridinium or imidazolium radical above meaning, wherein the alkyl radicals are optionally substituted on the nitrogen atom; Q ₂ represents a primary, secondary or tertiary amino group which may be part of a 5- or 6-membered aromatic heterocyclic ring, or an amidino, guanidino or hydrazino group, preferably dialkylamino groups, which may be substituted in the alkyl group; and Jr has the above meaning.

Of the basic disazo dyes which can be used according to the invention, those of the general formulas (3a) and (3b) are especially

QH

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(+) - B-U-Ar-H = U- i R 13th 4.1982 231 756/0 AP D 06 P / 59 370/11 2 Χ ⁽ "or x ⁽ ~) Q ₁ ⁺⁾ (or (3a) -Q ₂ ) -A ₁ -I = I-Ar-UBQ / R

(Q ₀ - od).

Q ₁ ⁽⁺⁾ -BN-Ar-lsr =: HA

I ι

(3b)

or or

to call, in which Ar, B, R, Q ^ »Qp ^urL ^ ^L ^ - <^ - ^e - ^ ² " have formula (1) or (2) meanings, wherein in the formulas (3) respectively each of two formula radicals may be the same or different from each other;

A- is the radical of an aromatic carbocyclic or aromatic heterocyclic tetrazo moiety, but in particular den'Phenylenrest, the Uaphthylenrest or the Diphenylenrest or one of the radicals of the formulas

wherein the aromatic nuclei in the above-identified members as well as in these two formulas may be substituted by substituents, preferably 1 or 2 substituents, from the group lower alkyl, such as methyl, lower alkoxy, such as methoxy, and chlorine;

A _{2 represents} the radical of an aromatic carbocyclic or aromatic heterocyclic tetrazo moiety having at least one quaternary moiety, in particular

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is part of a 5- or 6-membered Jaeterocyclisohen ring and wherein the heterocyclic and / or carbocyclic moieties are optionally substituted; D _{2 is} an aliphatic or aromatic carbocyclic or aromatic heterocyclic or simple atom grouping bridge member, for example one of the formulas -CH ₂ -, -CE ₂ CH ₂ -, -O-CH ₂ -CH ₂ -O-, -CH = CH -, -SLH-, -O-, -S-, -SO ₂ -, -U = N-, -UH-CO-HH-, -CO-HH-, -HH-CO-, the rest of the formula

CH.,

I * -C- or a cyclohexylene radical, or

CH, a heterocyclic radical, for example the formulas

H H H - H H H, H

H Il Il H H il - /

-C is C-, -C .C-, -C-C or ^ H

H, however, preferably a bridge member of the formula

-CH _{2 is} -CH ₂ -, -CH = CH-, -HH-, -SO ₂ -, · -CO-HH- or -HH-CO-; and in which

E represents a divalent bridge member of the formula -O-, -S-, -HH- or -SO ₂ -

In the above-described disazo dyes according to the general formulas (3a) and (3b), the formula radicals Qlj ' and Q ₂ - both together or individually individually alone - may also be bonded directly or only via the bridge member B to the respectively associated arylene radical Ar in which case, however, the selection rule is that a formula given in formula (3a)

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optionally existing radical Q ₂ can not be directly connected to Ar and that according to formula (3b) in the case of two mutually bound to the Ar directly radicals Q _2, the rest of the tetrazo component A _{2 must have} more than one quaternary group.

Of the basic disazo dyes which can be used according to the invention, in particular those of the general formulas (4a) and (4b)

2 2 ^(-) (4a)

-N = N-Za-NQ, -N- P b% -N = ND

R

(4b)

to call, in which D ^ are the same or different and each is as defined above; Q-2 is a lower alkylene group such as an ethylene or propylene group, a lower alkylene-oxy-alkylene group such as an ethyleneoxy-ethylene group, or a lower alkylene-amino-alkylene group such as a diethylene-amino group is, or is an alkylene group of 2 to 8 carbon atoms which is interrupted by two amino groups or oxygen atoms, such as a dioxy-triethylene group, or a lower alkylene group which is optionally substituted or by an aromatic carbocyclic radical, such as Benzene nucleus or naphthalene nucleus, for example by the m- or p-xylylene radical, by -0-CO-, -! (Alkyl) or -N (phenyl) - may be interrupted;

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R and Rp are the same or different and each represents a hydrogen atom or a lower, optionally substituted alkyl group, or IL and R ₂ together with the two nitrogen atoms and the radical Q 1 form a heterocyclic ring, such as a piperazine ring; The benzene nuclei a and b, Each may be substituted by one or two substituents selected from the group lower alkyl, lower alkoxy, halogen, tri fluorine thy I and lower alkanoylamino the same or different, or the cores a or b or both each with a fused benzene nucleus form a naphthalene radical;

and

has the abovementioned meaning.

"Of the basic methine dyes which can be used according to the invention, those of the general formula (5)

H ₃ C

-CH = CH-C a'V = H = qy-IF * / b ^λ Υ -CH-CH-C R ₁ R ₂

(5)

in which R ₁ , R ₀ , Q- ,, X as well as the

zolkerne a and Jb have the abovementioned meanings} R, a lower, optionally substituted alkyl radical or an aralkyl radical, for. B is the benzyl or phenethyl radical; and

U are both the same or different and each represents a hydrogen atom, a halogen atom such as a chlorine or bromine atom, a lower alkyl group such as a methyl or ethyl group, a lower alkoxy group such as methoxy or ethoxy

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group, a urea group, an aryloxy group such as a phenoxy group, an aralkoxy group such as a benzyloxy or ph. enathoxy group, or a lower carbalkoxy group such as a carbomethoxy or carbethoxy group.

Particularly suitable basic dyes according to the invention are azamethine dyes of the formula (6)

+) C-CH = CH-U-A ^ -U-CH = CH-C "" (+

and diazamethine dyes of the formula (7)

CH.

U R

2 X

(6)

(7)

2 X ^

to emphasize, in which R ₃ , ü and X ^ have the meanings given above;

R.sup.1 and R.sup.c are the same or different and each is a hydrogen atom or a lower, optionally substituted alkyl group;

and Ao represents a divalent radical selected from one or more aromatic carbo or heterocyclic nuclei

on / mn -mc η -i η η α Γ ·, 'ο

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which may still be interconnected by non-aromatic bridge members

The bivalent radical A-, for example, the bivalent heat of benzene, naphthalene, diphenyls, GlykoldiphenyΙα thers, Diglykoldiphenyläthers, a lower diphenylalkane, the diphenyl ether, the diphenyl sulfide, the diphenyl sulfone, the DiphenyIketons, the azobenzene and the Diphenylharnstoffs, where the benzene nuclei in these radicals may each be substituted by 1 or 2 substituents, preferably from the group lower alkyl, lower alkoxy, halogen, such as bromine and especially chlorine, carbamoyl and sulfamoyl »or A, is for example the bivalent radical of 2-phenylbenzimidazole , of 2-phenylbenzothiazole, of 2-phenylbenzoxazole or of diphenyl-oxadiazole, where the "heterocyclic ring may be substituted by lower alkyl groups, or A" is the bivalent radical of the formula

-Alkylen- N Alk- ^

in which Alk has the meaning of a lower alkyl radical and alkylene is a straight-chain or branched alkylene bridge member.

The process according to the invention is particularly advantageous, with the use of bis-quaternary dyes, in particular of bis-quaternary disazo dyes of the general formula (4a) in which D is identical or different.

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and each is an above-mentioned triazolium, benzthiazolium or thiazolium radical, Q is an alkylene group of 2 to 4 carbon atoms, R 1 and R _{2 are the} same or different and each is a lower, optionally substituted alkyl group , preferably a hydrogen atom and the benzene nuclei a and b_ and X have the abovementioned meanings, furthermore quaternary methine, azamethine and diazamethine dyes of the general formulas (5), (6) and (7), in which Q - ,, R ^, R ₂ , a and b, and X ^ ~ 'have the meanings just mentioned and ky R-, R, R ₅ and ü for the formulas (5), (6) and (7 ) have given meanings.

The process according to the present invention can also be carried out using methine compounds of the general formula (8)

CH.

-CH = CH-Ar-IB-QJj ^ ¹ (or -

(8th)

2 1> ^J or X- *

where Ar, B, R, R 1, Q 1, Q ₂ , U and meanings

the above

Furthermore, dyes which can be used according to the invention are in particular azamethine and diazamethine compounds of the general formula (9)

23 1 756 · * O

Alk

auk

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C-CH = Y-Z-H

0-alkylene-Z

In the formula (9) mean

Rg is an alkyl group of 1 to 4 carbon atoms, which may be substituted, for example by a carbamoyl group (-COUH ₂ ) »an alkanoyloxy group of 1 to 4 carbon atoms, a carbalkoxy group having 1 to 4 carbon atoms in the alkyl radical, a Hydroxy, cyano or phenyl group;

Alk is "an alkyl group of 1 to 4 carbon atoms, both of which may be the same or different; Y is the methine (CH) or nitrogen; Rj is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms which substitutes may be, for example, a carbamoyl group, an alkanoyloxy group of 1 to 4 carbon atoms, a carbalkoxy group having 1 to 4 carbon atoms in the alkyl group, a hydroxy, cyano or phenyl group; alkylene is a straight-chain or branched alkylene group of 2 to 6 C atoms, Z is a group of the formula (9a) or (9b)

- TSS '

rr

(9a)

(9b)

in which

Rg is an alkyl group of 1 to 4 C atoms, which are substituted

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may be tuted, for example by a carbamoyl group, an alkanoyloxy group of 1 to 4 carbon atoms, a carbalkoxy group having 1 to 4 carbon atoms in the alkyl radical, a hydroxy, cyano or phenyl group,

Rq is an alkyl group of 1 to 4 C atoms which may be substituted, for example by a carbamoyl group, an alkanoyloxy group of 1 to 4 C atoms, a carbalkoxy group having 1 to 4 C atoms in the alkyl radical, a hydroxy, cyano or phenyl, or the phenyl radical which is substituted by 1 or 2 substituents selected from the group chlorine, alkyl of 1 to 4 C atoms, alkoxy of 1 to 4 C atoms, Mtro, carbalkoxy having 1 to 4 C atoms in the Alkyl radical and carbamoyl may be substituted, and

R _{10 is} a hydrogen atom or an alkyl group of 1 to 4 C atoms, which may be substituted, for example, by a carbamoyl group, an alkanoyloxy group of 1 to 4 C atoms, a carbalkoxy group having 1 to 4 C atoms in the alkyl radical, a hydroxy -, cyano or phenyl group, or in which

R ₀ and R _n together with the nitrogen atom is a 5-, 6- or ο y

Form a 7-membered heterocyclic radical which may contain as another heteroatom, a nitrogen, oxygen or sulfur atom, such as the piperidine, piperazine, morpholine, pyridine or pyrimidine ring, or Rq and Rq or Rg, R _n and R- q form, together with the positively charged nitrogen atom, a 5-6-membered or 7-membered heterocyclic radical which may contain, as further heteroatom, a nitrogen, oxygen or sulfur atom, such as the piperidinium, morpholinium, piperazinium , 4-H-methyl-piperazinium or pyridinium radical, where Rq is either part of the heterocyclic radical or a hydrogen atom or the abovementioned alkyl

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can be group;

the benzene nucleus E can be substituted by 1 or 2, preferably one, substituents selected from the group consisting of halogen, such as chlorine and bromine, mercury, cyanogen, sulfamoyl, alkyl of 1 to 4 C atoms, alkoxy of 1 to 4 C atoms and carbalkoxy with 1 be substituted by 4 C atoms in the alkyl radical;

the benzene nucleus el may be substituted by 1 or 2, preferably one, substituents selected from the group consisting of halogen, such as chlorine, kyro, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and carbalkoxy having 1 to 4 carbon atoms in the Be substituted alkyl;

η is the number 1 or 2; And

X 1 is the equivalent of a colorless anion as defined above.

RQ radicals has the formula Rg, Hj ₁ "Rq, R, R ^ ₀ and Alk, as are the substituents of £ and d may each have identical or different meanings _q. Preferably, the same meaning as

The above-mentioned alkyl groups are preferably methyl and ethyl groups, the alkoxy groups preferably methoxy and ethoxy groups; Carbalkoxy groups are preferably carbomethoxy and carbethoxy groups, alkanoyloxy groups preferably the acetyloxy group.

Finally, mention should be made at this juncture of those bis-quaternary dyes which, in addition to an azamethine or diazamethine function, also have an azo grouping in their molecule, which have likewise been found to be useful for carrying out the claimed process.

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Further suitable dyes for the claimed process are, in particular, those from the class of the naphtholactam compounds corresponding to the general formulas (10) and (11)

ff.

(or -

or Σ ^κ (10)

Ir = G -Ar -ff- Q ₇ -N-aryl

^Λ 1

R ₂

(11)

highlight where Ar, B, Q-

'^ 2' ^ 3 '^' ^ I '^ 2 and X ^' 'with the meanings given above for

these substituents match ·

R ₃ , U

Finally, of the dyes which can be used according to the invention, those which are based on compounds of the general formulas (12) and (13)

(Q ₂ - or) Q ^ ⁺ ^ -BY ₁ -B-

(or -Q ₂ ) m X ^

(12)

and

231756

(Q ₂ - or) Q! J ⁺ ^ -BY ₁ -Bq! J ⁺⁾ (or - <

(or -Q ₂ )

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m X

(13)

in which Y represents the residue of a coloring matter chromophore, such as a copper phthalocyanine optionally substituted by chlorine or phenyl, an anthraquinone derivative, a Uitrofarbstoffes or a dye based on a triphenylmethane compound

dung; the other substituents B, Q

Q ₂ and P

" ^J

the

have the meanings mentioned above and m is 0, 1, 2 or 3 ·

The subject of the present invention is a process for dyeing fibrous material such as slivers. or yarns made from acid-modified acrylonitrile polymers in the gel state, which have been prepared by a conventional hemp spinning process. Due to the fact that the dyeing of the spun polymers of acrylonitrile according to the invention takes place from solvent-containing liquors, are washing processes in which the threads of which for the production The dyeing operation can be carried out without changing the equipment required and practical for the spinning and finishing of undyed yarns. In the context of the claimed process, using the basic solvents described in the above explanations Dyes are suitable dyebaths, which except water between 5 and 70 wt .-%, preferably between 5 and 50 wt .-%, but especially between 5 and 30 wt .-% of an organic solvent

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In this case, the unstretched, partially stretched or stretched fibers or filaments whose hydration state is between 5 and 150% of the weight of the polymer are preferably interspersed 30 and 120 % - without being dried at temperatures between 10 ° and 100 C, preferably between 20 ° and 90 ⁰ C, at a pH between 2 and 7, preferably 4 and 5 5> thus in the weakly acidic range with treats the dyes dissolved in the solvent-containing dyeing medium. The staining time is between 1 second and 10 minutes; Generally, it is dyed between 1 and 60 seconds, preferably between 3 and 20 seconds. The stated dyeing time corresponds to the residence times of the fibers in the dyeing liquor, through which the spun material passes after exiting the die and then taking place coagulation. In this case, the contact between the Acrylnitrilpolymerisat and the Färbeflotte can take place according to all practical procedures, such as in a dip trough, such as a padder · For optimum utilization of the dyeing liquor is possible, advantageously leads the dyeing liquor in countercurrent or in cross flow to the direction of movement of the fibers ,

According to the present invention, in the course of the dyeing, one equivalent of the acidic groups in the fiber substance combines with an appropriate amount of groups of the dye which behave basicly with respect to this group to form a salt-like bond.

The stretching of the fibers is carried out according to the method in the dyeing process itself or immediately afterwards.

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In addition, after dyeing, the fibers can additionally be treated with anionic or cationic plasticizers. It is also possible to attach a treatment with steam or hot air.

In addition to pH-regulating compounds, other chemicals are generally not required for carrying out the claimed process, but may be used for special purposes.

Since electrolytes interfere with many customary acrylonitrile gel dyeings, it is advantageous if the dyestuffs used according to the invention are used without electrolytes, ie that they are used particularly advantageously without large amounts of "thickening agent" or in the form of liquid adjustments.

The concentration of the dye in the dyebath depends on both the dye used and the shade and depth of color desired, and can range from a very low concentration to a saturated dye solution *

The dyeing operation itself can be carried out continuously or batchwise during the dyeing process. During dyeing, with the fiber material continuously passing through, the concentration of the dyebath is constantly maintained at the desired level by suitably adding a solution of the dyestuff at a concentration such that replaced by the slivers dye is replaced continuously. The thus dyed slivers or threads are then fixed under practical conditions with steam or hot air, stretched,

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aviviert.und optionally under the authorization of shrinkage dried, curled and placed in boxes. The achieved fastness properties, such as light, water, perspiration, dry and Haßreibechtheiten and'Überfärbeeehtheiten are flawless in all cases.

In addition to the polymers of acrylonitrile, copolymers of acrylonitrile with other vinyl compounds, such as, for example, vinylidene cyanide, vinyl chloride, vinyl fluoride, vinyl acetate, vinyl propionate, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylethanol, acrylic or vinylidene, come into use as substrates to be spun Acrylic or methacrylic acid esters, acrylic or methacrylic acid amides, these copolymers having at least 50 wt .-%, preferably at least $ 5 wt .-% acrylonitrile units. The homopolymers of acrylonitrile or its copolymers used are acid-modified; they contain at least one acidic function, such as, for example, sulfo or sulfato groups, which are respectively introduced into the end of the polymer chains by means of a catalyst, or comonomers containing acidic groups, such as e.g. For example, acrylic acid, itaconic acid, vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, vinyloxyarensulfonic acid, allyloxyarensulfonic acid, Methallyloxyarensulfonsäure, Acryloxyalkoxyarensulfonsäure and their alkali metal salts, were polymerized »

Thus, according to the invention, all acrylonitrile polymers which contain acidic groups capable of binding the basic dyes used are suitable. Such acidic groups are present in the spun material in amounts of between 10 and 150 milliequivalents per kg of polymer, preferably between 20 and 80 milliequivalents per kg of polymer.

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The described Aerylnitrilpolymerisate can be spun from all practical solvents on an organic basis, followed by the dyeing with the dyes of the invention, preferably from the same organic medium followed. For the spinning process and the subsequent dyeing operation as suitable solvents are dimethylformamide, DimethyIacetamid, Äthyiencarbonat, ß-butyrolactone, tetramethylene sulfone, DimethyIsulfoxyd and other polar, aprotic compounds in question.

In the wet-spinning procedure carried out in the present case, the dissolved polymer is spun into a coagulation bath which, in addition to the solvent used for the dissolving polymer, still contains about 30 to 70% by weight, preferably 40 to 60% by weight of water; after the coagulation bath, the threads thus spun can pass through a drawing bath which still contains about 30 to 85% by weight, preferably 40 to 85% by weight of water; then follows z. Example, a washing bath, the still-over-70 wt .-%, - preferably to over 80 wt .-%, or consists entirely of water. As already mentioned above, the stretching measures in the claimed method can also take place during the dyeing operation or subsequently.

The age of the spun material does not play a major role in the process of the present invention. Both freshly spun fiber tow and spun material, which was 3 months old and stored in sealed cans, showed the same deep staining and complete staining of the fibers after the staining process.

The following examples serve to illustrate the invention. The parts and percentages stated therein

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are parts by weight and percentages by weight, unless otherwise stated. Volume parts behave to parts by weight like liters to kilograms.

Example 1: .

An acrylonitrile MisGhpolymerisat of 94 % acrylonitrile, 5 % AcryIsäuremethy1ester and 1 % Ha-Methallylsulfonat is wet spun in the form of a 28% dope in dimethylformamide under standard conditions at 80 ⁰ C using a 100-hole spinneret with a hole diameter of 80 / in which a coagulation bath of 50 C is used, which consists of 50 % dimethylformamide and 50 % water »

The yarn material obtained is then without prior drying in a Henge of 10g (dry weight), corresponding to 20 g Feuehtgewicht, for 60 see. with good liquor movement in a solution made by means of acetic acid to pH 4.5 from 0, -Ot-g of a bis-c [uartären- dye of the formula _;

placed in 250 ml of a solution of 20 % dimethylformamide and 80 % water from room temperature. Wake up the specified residence time of the spinning material in the dyeing liquor observed a virtually complete Baderschöpfung. The treated threads are then ge with water

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  rinses, stretched as usual, relaxed and dried.

Man.erhält a bluish red color with excellent fastness properties, mainly particularly good Uaßechtheiten and very good light fastness *

Example 2:

If a solution of 0.05 g of the dyestuff mentioned therein in 100 ml of a solution of 40 % dimethylformamide and 60% of water is used in the dyeing of Example 1 and a dyeing time of 10 seconds is maintained, a strong dyeing is likewise obtained the Fadenmaterial3 with excellent fastnesses *

Shortening the dyeing time even further up to 3 ounces, one obtains probably a somewhat lighter color, but with likewise excellent fastnesses and with complete staining of the thread material over the entire fiber cross section.

Example 3?

Passing ^the: thread material of Example 1 continuously (as filaments) by the method used in Example 2 dyebath, wherein no special coagulation bath upstream (ie coagulation in the dye bath), and a residence time of the filaments in the dye liquor of 3 lake. is set and with an aisle of the current thread of 2 min * followed by room temperature, the so dyed fabric rinsed, stretched, relaxed, scavenged and then dried, we obtain an equally good dyeing result as in Example 2. The rinsing and conditioning baths be through this

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the dye used not appreciably bleed.

By maintaining a residence time of .2 see and otherwise same conditions will be a slightly brighter, from 10 see. a. achieved darker coloration.

Example 4:

In the case of the dyeing process described in Example 1, after the dyed yarn material has been taken, the product is treated for 30 seconds in a solution of 0.5 g of a plasticizer of the formula

Stearyl

CH

Cl

in 100 ml of water from room temperature ah, "this avivage does not lead to any bleeding of the dye into the applied cleaning bath ♦

Example 5 i

If the polymer of Example 1 is used, but this is spun here using dimethylacetamide as solvent in a wet spinning process which is customary in practice, the dyeing described in Example 1 can be carried out with the same good result using the spinning stock obtained in this manner. Dye fixation is just as fast and complete.

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Example 6 ι

If the polymer of Example 1 is used, but this is spun here using ethylene carbonate as the solvent in a wet spinning process which is customary in practice, the dyeing described in Example 1 can be carried out with the same good result using the spinning stock obtained in this manner. Dye fixation is rapid and complete.

example 1'.

If the polymer of Example 1 is used, but this is spun here using dimethyisulfoxide as solvent in a wet spinning process which is customary in practice, the dyeing described in Example 1 can be used to carry out the dyeing described in Example 1 with an equally good result. Dye fixation is rapid and complete.

Examples 8 to 14:

Substituting now the polymer used in Example 1 by other polymers having the following composition, is also obtained with the obtained in this manner in accordance with the spinning material Färb§vorschrift ^v of Example 1, a very rapid and firm fixing Färbstoff:

3aAPR.1932 * O (K) 5!

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Example of polymer

94% acrylonitrile

4% Acryisäuremethylester 2 % Na-Methallylsulfonat

95 % acrylonitrile

4.5 % methyl acrylate

0.5 % acrylic acid

85% acrylonitrile

13 % vinyl chloride

2 % Ua-allylsulfonate

85% acrylonitrile

14.5 % vinyl acetate

0.5 % Na vinyl sulfonate

59 % acrylonitrile

40 % vinylidene chloride

1 % Ua-methallylsulfonate

1.3 94 % acrylonitrile

5 % methyl acrylate

1 % styrene-4-sulfonic acid Na

94% acrylonitrile

4% vinyl acetate

1 % Wa-methallylsulfonate

1 % itaconic acid Na

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Example 15;

If, instead of the yarns produced according to Example 1, such threads are added to the spinning process, 0.2 parts of a commercially available titanium dioxide matting agent (based on the polymer), so obtained in dyeing the spinning material according to the procedure of Example 1 also one good dye fixation and very good fastnesses ·

Examples 16 and 17:

One works in the dyeing of the spun material instead of that of Example 1 at a dyeing temperature of 60 ⁰ C or · 90 ^ 0, but otherwise under identical conditions, we get one, same: deep Ahfärbung of the threads at · the same, good fastness properties.

Example 18t - -.-

If, instead of used in Example 1 ¹ strand material is a yarn material of identical polymeric composition comprising (= -10 g) at the same dry weight, but a wet weight of 25 g (. D · h a highly hydrated material) so it behaves; , also a very good dye fixation on the spinning material, if one works for dyeing according to the instructions of Example 1.

Example 19:

Is used for dyeing instead of the dye used in Example 1 here is a conventional mono-quaternary

231756

ren dye of the formula

13 x 4 x 1982

AP D 06 P / 231 756/0 59 370/11

Ν-Ι-ί

ell - -r

₁ J -

ZnCl.

so laxv'auf the spinning material according to the operation el &*; For example, only a very incomplete dye fixation, that is to say, a very large part of the dyestuff remains in the dyebath, and in this case an increase in the dyestuff fixation can not be achieved by prolonging the residence time.

In contrast, the dyeing of the same thread material with the bis-quaternary dye of Example 1 results in a very extensive exhaustion of the dyeing liquor already after the usual dyeing time.

Examples 20 and 21:

Substituting for dyeing the spun with the bis-quaternary dye of Example 1 instead of the dye amount of 0.01 g used therein, amounts of 0.03 g and 0.001 g of the same dye, we obtain according to the procedure of Example 1 in the present dyeing test correspondingly increased or decreased color depth an equally rapid and solid dye fixation. The fastnesses of the dyeings are also very good.

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Examples 22 and 23s

If, in the course of the procedure of Example 1, the freshly spun thread material after coagulation is washed in such a way that a residual content of 8 % or »20 % of the dimethylformamide used as spinning solvent remains in the spun material used for dyeing in the staining operation after the local Torschrift also a very high dye fixation »

Examples 24 and 25?

If the dyeing of Example 1 is carried out here at pH values of 3 or 6 instead of at pH 4.5, but otherwise under the same working conditions, the same dyeing result is obtained as in Example 1.

Example 26:

If one works in the SFaßver spinning of the polymer according to the instructions of Example 1, but stretched the recovered thread material, before the actual dyeing process in a conventional manner in the ratio of 1: 1.5, ie by 50 % ·> so when dyeing after " Example of Example 1 also a very good dye fixation.

Example 27:

If you work for dyeing according to the instructions of Example 2, but under the leadership of the thread material in the opposite direction. to the stream, the dyeing liquor, whereby a tubular bath of color is used, a complete achievement is achieved.

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Creation of the dyebath, that is, by the very good dye fixation occurs after the residence time of a dye largely freed from residual dye bath.

Example 28:

If the dyeing described in Example 3 is carried out with simultaneous stretching of the thread material in the ratio of 1: 3, the result is the same dyeing result as in Example 3.

Example 29:.

If, in the procedure of Example 1 for dyeing the spinning material, a mixture of dyes is used in the quantities indicated below:

0.005 g of dye of the formula

CH

CH-

-Έ

CH.

CH.

CH,

CH 3_

2 ZnCl,

2317 56

0.003 g of dye of the formula

CH.

13 * 4.1982

AP D 06 P / 231 756/0

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CH.

OH

= CH-UH- / ~ V O - / "V-IiH-CH =

CH

ZnCl _;

0.002 g of dye of the formula

CH.

CH ₃ O '

^ _s j3_K == ij-

.CH.

'CH ₂ -CH ₂ '

CH.

OCH

ZnCl

so ^i: get mari 'eihe ^; Dye deep brown dyeing with very high fastnesses, especially with very high light fastness, wash fastness and alkaline perspiration fastness.

Example 30 and 31 '*

In the procedure of Example 1 after the actual dyeing and rinsing of the thread material with water still a steaming process of the same, during 20 min <>. at ca <> 102 ⁰ C or «1.0 min. connected at 115 ⁰ C, we also get a very good staining result ο

.- -. ™ t ^ ιΠ O

... η η ii K. C »

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Table examples '

If, instead of the dye used in Example 1, other dyes of the following formulas are used for dyeing the spun material, a very good dye fixation is also obtained, while maintaining otherwise identical conditions. a good BaderSchöpfung and a very high level of authenticityi

example

32

formula

0-CH ₂ -CH ₂ -IK

CH.

33

2 cl

34

nuance

reddish

blue

bluish

violet

blue-

2BF

violet

13 · 4.1982

AP D 06 P / 231 756/0

59 370/11

vj

he"

VJJ Ul

VJJ CQ

Η · O I- ¹

CD

et

ct

txl

H- O

O c +

f- * CD

CD et

c + H ·

et o

tS3 13 Ω

ΓΟ

Η · O M CD

c +

ct

9 S Z I €

ΙΛ

CNJ

ιη

Example 38

CH.

NFN

Formula 0-CH ₀ -CH ₀ -IK (

IC. C.

CH.

39

CH,

Ιί

1 CH

CH.

N-CH ₂ -OH ₂ -H (OH ₃ )

CH ₃ SO ₄

40 (CH ₃ ) ₃ N-CH ₂ -CO- / Vn = N- ^ N-CH ₂ -CH-CH ₂ -N (C ₂ H ₅ )

'2 ¹ V 2

CH.

OH

nuance

bluish red

yellowish red

red

U) τ- ΙΓν _τ - ΟΛ CVJ O CVJ Ir ω ν- ο O * φ ί-1

ιη

example

41

(CH

formula

N = W

Cl

Nuanc e

CI

orange

42

43

CH

3 .CH

OO

CH.

^ CH = CH-NH- /

O-CH ₂ -CH ₂ -N (CH ₃

CH ₃

Ij ί ^GH 3 N-

CH

0-CH ₂ -CH ₂ -N (GH ₃ ) ₂

CH ₃ COOH

yellow

reddish yellow

VD ITv

CVl P4 x-

oo t-

Ch VO ^ ¹ · »

T-OO

cn

in

Example 44

formula

CH = N-N-

CH-

BP,

HCl

Nuanc e

reddish yellow

reddish yellow

46

CH.

Cm

CH.

CH = CH-NH

CH.

• Ο (h-) nh (ch ₃ ) ₂

ZnCl,

yellow

04/13/1982

AP D 06 P / 231 756/0

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VX)

CO

Η ·

CD

CB O

M eggs OQ

ro

UI

ro

W U)

ro

S3 Ω

ro

ul

ffi

13 · 4.1982 Ul O 756/0 AP D 06 P / 231 59 370/11 example

fO

ro

U)

P =

C +

03c + H-O

tr

H-

0 <3

Ω H

CW CD

ro i

he

13 · 4 «1982

AP D 06 Ρ / 231 756/0

59 370/11

VJl Ul

 W

te)

I - Ω I ro ! • fc * ro ι Ω Ω   a W UI ro vj k vj ro IS! Ω +

W Φ Η · UI CD vj Η · Φ

I SEj + vj Ω U) W Ω H } Ω -SEJ V // Ω-t3 W V W / \ ro ω

 e

hi O

σο

hiCW φ

13 * 4.1982

AP D 06 P / 231 756/0 59 370/11

VJI

VJL

CD

πω * ö

H-CD H ¹

CD Η ¹

c +

is ο CD

ν CVI

CM Ph t-Cr \ V £> ^ -

v-OO

• C-

-si- Ω c * \

γ * Λ Ph er »

example

59

formula

nuance

60

61

CH-

-'TFJU *

JJ

CH ₂ CH

OH ₃ -

OH,

CH-

= N- (v> -N-CH ₂ -CH ₂ -N (

CH, CH ₂ -CH ₂ -NC CH ₃ ) ₂

Cl

violet

_blue

red

ν J

- Ω U)

13 * 4.1982

AP D 06 Ρ / 231 756/0

59 370/11

u>

! si - Ω

W ro

ro

Ω O I

ro

Ω O

ro

ul

CSl 13 Ω

ro

he M

is ο φ

f * η Γ ι ι

he.

13th 4.1982 756/0 AP D 06 P / 231 59 370/11 example ΟΛ VJI vj

Hi he t i Ω i ro 05 ro Ω JS vj ffi i CQ VjJ Ω ch O H· O O tr I

Oh hi

(3 CR O)

he

Pu

vj

CO +

vj

hi B

(D

example

Formula Nuano e

LA C

CVJ

OJ Ph χω r- (Ti U) N t -OO • C-

68

(Λ

"A; in

69

70

, ^CH CH.

CH ₃ H ₅ C ₂

= N- {Vn- (CH ₂ ) ₂ -N- (0H ₂ ) ₂ -N

CH.

CH.

CH-

- (CH

BF

violet

CH.

CJH _t

BF

4 blue

BF,

bordo

C ₂ H ₅

-α ro 13ο 4 * 1982 756/0 AP D 06 Ρ / 231 59 370/11 Step Example W - ro

co

ro

ι- ·

CSI! 3

ro

C + hi ρ: (3

C +

QC / ι

νη

04/13/1982

AP D 06 P / 231 756/0

370/11

ro Ω

ro

CFQ

CT

CD e +

Q ς / Λ Γ ?.

0Λ CVI

(M ft r

ω r

CT \ VO \

τ- O O

^ P ΟΛ

(Λ Ρ4 CTv

r- <C in

example

77

78

CH ₃

CH.

  OH.

N = N

3 ^; ι CH-

formula

~ (CH _Q ) _o - O- (OH ₉ ) ₉ -N-

~ V-N = N

CH ₃

CH

^J

Cl '

CNS ¹

'N I

CH. Cl ¹

nuance

reddish purple

yellowish red

red

04/13/1982

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59 370/11

DG

ro

fei-fei

ro

fei-fe!

DG ω O CD Η · Ω ω W Η · (7 (D V> - ' ^Η Ω- ^fe W

tr)

Φ "

H- ¹

O H

H H-d-CT (Jq CD

(TT

U)

ω ro

S "Ω IU)

"Η

e +

example

formula

Nuanc e

t

CM

CvJ Ph τω τ-

ο

<Λ

cr>

83

Cl

CH ₀ -CH ₀ W

Cl ¹

yellowish red

84

CH-

-CH

CH = CH-NH

CH.

- (CH _{0) O} N -

SO,

 green

85

CH

CH.

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CH,

'/ Λ

CH.

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N- (CH ₂ ) 3 -N- / V NH-CH = CH ^

CH.

yellow

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86

formula

^l 3

CH. N-

CH

Nuano e

blue

87

CH

N-I CH,

C ₂ H ₅

CH = CH- <VN-CH ₂ -CH ₂ -N (CH ₃ ).

ZnCl ^£

red

88

CH = N-N-.

0-CH ₂ -CH ₂ -N (CH ₃ ) ₂

Cl '

orange

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89

90

91

formula

CH

CH.

CH ₃

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Cl

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CH>, -

(+) - CH = CH ^ N ^

I CH

CH.

CHO

Nuanc e

reddish yellow

Cl

(-) red

red

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example

92

CH

Ν ^ ₍ 3

formula

H ₃ C-

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T +)

CHi ₁

nuance

2 scr

reddish

yellow

93

94

CH.

CH,

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I C.

CH

CN

CH ₃ CH

! H = CH-NH

CH,

CHj

NH-CH = CH

^ S

S ⁺ H

C ₂ H

2 Cl ¹

yellow

Bi ¹

reddish yellow

 si "

.VD

13th 4.1982 P / 231 756/0 AP D 06 1 59 370/1 VD AJl example

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98

formula

nuance

100

(CH.J ^ N-- CHp-CO- / Vn = N- / VNH-CHp-CHp-N (CH-)

^ i) -j "" 2

Cl

Cl ¹

(+) CH.

Cl ¹

Cl

N = N

CH -, - ³ BF

reddish

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red

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13.4 * 1982

AP D 06 Ρ / 231 756/0

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Claims (12)

He proposes h 1. A process for dyeing in the course of the production process of a wet fiber spinning process produced from acid-modified polymers or copolymers of the acrylonitrile, in the gel state and optionally before the final orientation, with solutions of the acidic groups of the fiber substance "" " basic colorants containing not only water, but also a higher content of an organic solvent, especially of the solvent used to spin the polymer, characterized in that: the dyes used in their molecule are more than those of the acidic ones Having groups of the fiber substance basic behaving group. 2. Method near point 1, characterized in that the basic behaving groups in the dye molecule are quaternary groups. 3. Method according to item 1, characterized in that the basic groups in the dye molecule are a quaternary group and additionally one or more aliphatically bonded, primary, secondary or tertiary amino, guanidino, amidino or hydrazino groups. 4. Method according to item 1, characterized in that the basic groups in the dye molecule are more than one aliphatically bound, primary, secondary or tertiary amino, guanidino, amidino or hydrazino group. 5317 56 o   - 69 AP D 06 P / 231 756/0 59 370/11 Process according to one of the items 1 to 3 », characterized in that the basic dyestuff is a monoazo dye of the general formula (1) r ⁺ \ -N = NK X ^ "* 'or 2 X, if K is a - contains quaternary group, used in which D ^ ⁺ 'represents the radical of an aromatic carbo- or heterocyclic diazo component having a quaternary group, in particular a cycloammonium group as a constituent of a 5 * " or 6 membered aromatic heterocyclic ring, optionally with an aromatic carbocyclic radical directly attached or fused thereto, such as a benzene or naphthalene nucleus, which rings may be substituted in the heterocyclic and / or carbocyclic moieties, or an optionally substituted, aromatic carbocyclic or heterocyclic radical, such as a benzene, naphthalene or benzthiazole ring, directly attached or via a K is the radical of an aromatic carbo- or heterocyclic coupling component, in particular from the benzene, naphthalene or indole series, with at least one, to the core directly or via a Brükkenglied, aliphatically bonded primary, secondary or tertiary amino group or a (quaternary) ammonium group, optionally as part of a 5- or 6-membered aromatic heterocyclic ring (optionally cycloammonium), an amidine, guanidines, hydrazine or a Thiuroniumrestes, said rings in the heterocyclic and / or carbocyclic parts may be substituted; and 231756 O 13 x 4 x 1982 AP D 06 Ρ / 231 756/0 59 370/11 X 'is the equivalent of a -ΆΆΐΐ of my ^ strong inorganic or organic acid © that of a double salt " 6. A method according to item 5, 'characterized in that i -basischen as "dye> a-azo-Mon © ^Far; bstoff general formula (2a) -N = U-Ar-UBQ ₁ ^ ⁺ ^ (or -Q ₉ ) (2a) or X ^ or the general formula (2b) -K = I-Ar-OBQ ₁ ⁽⁺ '^; (or -Q ₂ ) (2 B.) or or: the general formula (2c) ^ ⁰ 2 X ' (2e) used in which D ^ and X ^ "^ have the meanings given in point 5; D _{1 represents} the radical of an aromatic carbo- or heterocyclic diazo component, in particular of the benzene or uraphthalene series, which may contain basic and / or preferably non-ionic substituents; Ar represents a p-phenylene or 1,4-naphthylene radical which may be preferably substituted by 1 or 2 nonionic substituents; R represents a hydrogen atom or a lower, optionally substituted alkyl radical, an aralkyl or cycloalkyl radical; 231756 O 04/13/1982 AP D 06 P / 231 756/0 59 370/11 B is a divalent aliphatic bridge member, in particular an alkylene radical of 1 to 6 C atoms, or a lower alkylidene radical; Q- for. a (quaternary) ammonium group, hydrazonium group or a cyclammonium radical as part of a 5- or 6-membered aromatic heterocyclic ring; and Q _{2 is} a primary, secondary or tertiary amino group which may be part of a 5- or 6-membered aromatic heterocyclic ring, or an amidino, guanidino or hydrazino group Process according to one of the items 1 to 3, characterized in that the basic dye used is a diazo-dye of the general formula (3a) -BN-Ar-K = WA ₁ -N = U-Ar-UBQR (3a) R (or -0 _o ) VO
IA
C- CVJ
\ CV ifh χω ν-σ \ ve \
 ν-ΟΟ (Λ "Sj LA CVI
C- CD ro Xi (ΰ U O C! φ ci • Η ω θ r-I CD α> ! 4 'Ο (Q ₂ - or) Q ₁ -N = N-Ar-N-B-Q. R (3b) (or - 3 Χ ^ν ' or 2 X ^ or X ^ 23 1756 O 13 x 4 x 1982 AP D 06 Ρ / 231 756/0 59.370 / 11 used, in which Ar, B, R, Q ₁ ' and Ir ""' have the meanings mentioned in points 5 and 6, wherein in the formulas (3a) and (3b) in each case doubly occurring formula radicals in each case the same or different from each other could be; A _{1 is} the radical of an aromatic carbo or heterocyclic tetrazo moiety; A _{2 represents} the radical of an aromatic carbo- or heterocyclic tetr-az component having at least one quaternary moiety, especially as part of a 5- or 6-membered aromatic heterocyclic ring; ''' and where the formula radicals Q ₁ ' and Q ₂ - both together or individually individually - can also be bound directly or simply via the bridge member B to the respectively associated arylene radical Ar, but then the selection rule is that a formula ( 3a) __ optionally present radical Q ₂ can not be directly connected to Ar and that according to formula (3b) in the case of two mutually bound to the Ar directly radicals Q _2, the rest of the tetrazo component A must have more than one quaternary group. 8. Method-nah point 7, characterized in that as a basic dye, a diazo dye of the general formula (4a) (4a) 17 56 0 13 x 4 x 1982 AP D 06 Ρ / 231 756 / G 59 370/11 or the general formula (4b). -0-Q, - 0- 2 X ^(-) (4b) used in which D ^ are the same or different and each D - and also X ^ "^ have the meanings given in point 5; Qu represents a lower alkylene radical which is optionally interrupted by -O-, -mi- or an aromatic carbocyclic radical; R and R _{2 are the} same or different and each represents a hydrogen atom or a lower, optionally substituted alkyl group, or R and Rp together with the two nitrogen atoms and the radical Qu form a heterocyclic ring; and the benzene nuclei a and te may be substituted by 1 or 2 nonionic substituents, identically or differently, or the benzene nuclei a or b_ or both in each case form a uraphthalene radical with a fused benzene nucleus. 9th Method according to one of the items 1 to 3, characterized in that as the basic dye is a methine dye of the general formula (5) 231756 13 x 4 x 1982 AP D 06 Ρ / 231 756/0 59 370/11 in which Q ,, R, Rp, a and b_ and X ^{v J have} the meanings given in points 5 and 8; Ro is a lower, optionally substituted alkyl or aralkyl radical; and U are both the same or different and each represents a hydrogen atom or a non-ionic substituent. , 10. The method according to one of the items 1 to 3, characterized in that as basic dye an azamethine dye of the general formula (6) H ₃ C < 2 X ^v or a diazamethine dye of the general formula (7) 231756 O -R.  CH, AP D 06 P / 231 756/0 59 370/11 2 X in which R 1, U and X 1 '' have the meanings given in points 5 and 9, A o is the bivalent radical of one or more aromatic carbo- or heterocyclic nuclei, which is further bonded by non-aromatic bridge members. and R and Rc are the same or different and each represents a hydrogen atom or a lower, optionally substituted alkyl radical. 11. The method according to one of the items 1 to 3 »characterized in that as the basic dye is a methine dye of the general formula (8) CH -CH = CH-Ar-K-B-Q- (or -Q ₂ ) (8th) 2 X <-> or X ⁽ where Ar, B, R, R ,, Q ,,, Q ₂ , U and I>'''have the meanings given in items 5 »6 and 9» 12. The method according to one of the items 1 to 3 »characterized by using as the basic dye an azomethine or diazomethine dye of the general formula 231756 O 13 x 4 x 1982 AP D 06 Ρ / 231 756/0 59 370/11 mel (9) (9) used in which M has the meaning given in point 5; Rg is an alkyl group of 1 to 4 C atoms, which is non-ionogenic? may be substituted; represents; Alk Each represents an alkyl group of 1 to 4 carbon atoms, both being the same or different from each other; Y represents - the methine radical (CH) or a nitrogen atom, R _{7 represents} a hydrogen atom or an alkyl group of 1 to 4 C atoms, which may be non-iono-substituted; Alkylene is a straight-chain or branched alkylene group of 2 to 6 carbon atoms; Z is a group of the formula (9a) or (9b). IL (9a) (9b) means in which Ro is an alkyl group of 1 to 4 carbon atoms, which may be nonionic substituted, Rq is an alkyl group having 1 to 4 carbon atoms, which may be non-ionic, © is the phenyl radical, 231756 O 04/13/1982 AP D 06 P / 231 756/0 59 370/11 optionally with 1 or 2 non-ionic substituents th, R | ₀ atom ein'Wasserstoff / ^or; an: Alky! group · ^; νοη is 1 to 4 carbon atoms, which are nonionic substituted can, .... or in which Rg and Rq together with the nitrogen atom form a 5- »6- * or 7-membered heterocyclic radical, or and Rq or Rg, and R-q along with the positive charged nitrogen atom form a 5-> 6- or 7-membered heterocyclic radical, wherein R- _o may be either part of the heterocyclic radical or a hydrogen atom or said alkyl group /; the Behzolkerne c and d may each be the same or different substituted by 1 or 2 non-ionic substituents, and
η stands for the number 1 or 2. 13 »Verfahren.nach one of the points 1 to 3t, characterized in that as a basic dye a liaphthalac · tam dye of the general formula (10) or (11) - Ar - B - Q ₁ ⁽⁺⁾ (or or (10) ! 31756 O - Ar - N - Q -. 13 * 4 * 1982 AP D 06 P / 231 756/0 59 370/11 2 X ^v (11) used in which Ar, B, Qi " ¹ "', Q ₀ , Q ,, R, R ₁ , R ₀ , R, ü and Ί>' have the meanings given in points 5, 6, 8 and 9 and wherein the substituents which occur in each case in formula (II) may be identical or different from one another 14 »method according to one of the items 1 to 4, characterized in that as the basic dye is a compound of general formula (12) or (13) (Q ₂ - or) -BY ₁ -BQ (or - (12) i (Q ₂ - or) Q ₁ -B-Y - B- (»ι B
t (or -Q ₂ ) (or -Q ₂ ) m X ⁽ ~ ⁾ (13) used in which B, Q ₁ , Q ₂ and X ^{v have} the meanings given in points 5 and 6 and in which the substituents which are in the formulas (12) and (13) g.: may be the same or different ; Y _{1 represents} the residue of a dye chromophore, in particular based on a copper phthalocyanine, anthraquinone or triphenylmethane compound; and 231756 m is G, 1, 2 or 3. 13 · 4 * 1982 AP D 06 Ρ / 231 756/0 59 370/11 Process according to one of the items 1 to H, characterized in that mixtures of these basic dyes are used.