DE1133695B - Leveling agent in textile dyeing - Google Patents

Description

INTERNAT. KL. D 06 p

GERMAN

PATENT OFFICE

B45256rVc / 8m

REGISTRATION DATE: JULY 10, 1957

NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: JULY 26, 1962

It has been found that compounds with two or more lactam residues in the molecule, which by Carbon chains are connected to each other, which carbon chains are connected by at least one oxygen atom, by a sulfoxide or sulfone group or by an optionally with an alkyl group no more than 3 carbon atoms, an aliphatic acyl group containing no more than 3 carbon atoms or imino group substituted by an aromatic acyl group are interrupted, exceptionally good ones Have properties as a leveling agent.

Compounds of the type mentioned are obtained, for. B. by implementing sym.-dichlorodimethyl ether or sym.-dichlorodimethylthioether or the corresponding Ethyl ether with lactams, ζ. Β. with pyrrolidone, caprolactam or caprylic lactam, or by reaction of tri- (chloroethyl) amine with the lactams mentioned or by reacting polyalkylenepolyamines, such as diethylenetriamine, triethylenetetramine or the corresponding propylene derivatives, with lactones like butyrolactone. The thioethers can be known before or after the reaction with the lactams Way to be converted into sulfoxides or sulfones. Instead of the simple lactams or lactones you can also lactams or lactones substituted on carbon, e.g. B. by lower alkyl or cycloalkyl radicals substituted, can be used for the implementation.

By reacting butyrolactone with diethylenetriamine you get z. B. the connection

R-CH ₂ - CH ₂ - NH - CH ₂ - CH ₂ - R

By reacting butyrolactone with dipropylenetriamine, z. B. the connection Leveling agent in textile dyeing

Applicant:

Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen / Rhein

Dipl.-Ing. Bjarne Hartmark,

Hambach (a. D. Weinstrasse),

Dr. Curt Schuster and Dr. Kart Herrle,

Ludwigshafen / Rhein, have been named as inventors

tin

V-- Γίη

Cycloalkyl-HC CO

R-CH ₂ -Ch ₂ -CH ₂ -NH-CH ₂ -CH ₂ -CH ₂ -R

By reacting butyrolactone with triethylenetetramine, z. B. the connection

R-CH ₂ -CH ₂ -NH-CH ₂ -Ch ₂ -NH-CH ₂ -CH ₂ -R In the formulas, R can e.g. B. mean H ₂ C CH ₂

H.C

CO

H ₂ C CH ₂

Alkyl — HC CO

N "

It can be said quite generally that the dyeing auxiliaries used according to the present invention Contain at least two lactam residues in the molecule, plus at least one outside of the lactam residue per molecule one heteroatom and at least one additional carbon atom per lactam residue. In the molecules however, there can also be more additional carbon atoms or two or more additional heteroatoms each lactam residue are located.

In addition to the lactam derivatives described in detail above, it is also often possible to use the products further modified by the addition of low molecular weight organic residues are used. For example, by alkylation or acylation of nitrogen as an additional heteroatom containing lactam derivatives obtained products with a modified retarding effect. Alkylated or acylated with aliphatic radicals containing a maximum of 3 carbon atoms or with benzoyl. For the alkylation are haloparaffins, and the acylation are carboxylic acids and sulfonic acids and their derivatives such as acid halides and esters. You get particularly effective products if you at least two molecules containing at least two lactam residues and at least one NH group with dihaloparaffins or aliphatic dicarboxylic acids containing not more than 5 carbon atoms

209 627/294

or implements their derivatives. In this way, compounds containing at least four lactam residues are obtained contained in the molecule and have a particularly favorable leveling effect.

Compounds suitable for substitution on the nitrogen atom are, for. B. ethyl chloride, ethylene chloride, Dichlorodimethyl ether, acetyl chloride, propionic acid chloride, the dichloride of succinic acid, chlorides of aliphatic sulfonic acids containing not more than 3 carbon atoms or the esters thereof Acids. In addition, alkylene oxides, in particular ethylene oxide, can also be used for alkylation on the nitrogen atom to be used.

The dyeing auxiliaries according to the invention have an excellent leveling effect during dyeing z. B. with vat dyes, sulfur and disperse dyes and nouns dyes. The means on the other hand do not have any pronounced surface-active properties; they do not foam and wetting in the concentrations required for leveling. You can in the presence of the dyeing auxiliaries described dye, but you can also use it for an equalizing post-treatment of uneven dyeings. The agents can be used in amounts of 0.1 to 20 g per liter, preferably 1 to 3 g per liter will.

It is known that pyrrolidone itself and substitution products of pyrrolidone, but that always contain only one pyrrolidone residue in the molecule, as a dyeing aid, especially as a leveling agent, be used. However, it could not be presumed that those used in the present invention Lactam derivatives would show several times the abundance of the most effective Coloring auxiliaries that contain a single pyrrolidone residue in the molecule. On the other hand, it is very remarkable that the lactam derivatives used according to this invention are none or one in comparison to those previously customary leveling agents with affinity for dyes exert a noticeably low retarding effect on the dyestuff. It has also been reported that the reaction product of butyrolactone and diethylenetriamine, acylated with aliphatic radicals containing at least 6 carbon atoms, Netz-, Schaumund Shows cleaning power and therefore used as textile auxiliaries, e.g. B. used in dyeing and leveling can be. However, these products stand behind the substances used according to the invention back.

The preparation of the addition products of butyrolactone with the polyalkylenepolyamines is according to The following regulations, in which parts are parts by weight, are possible:

I. 206 parts of diethylenetriamine (2 moles) are gradually mixed with 387 parts of butyrolactone (4.5 moles) with stirring. Strong warming occurs in the process. The mixture is maintained 4 hours at 230 ° C and further 2 hours at 250 ⁰ C. During this and then in a vacuum of 5 mm, volatile constituents up to 130 ° C. are distilled off. 453 parts of the desired dilactam are obtained as a viscous, brownish, water-soluble liquid.

By benzoylating in the usual manner with 1 mole of benzoyl chloride, that in the dilactam any secondary amino group still present is acylated. A water-soluble viscous one is obtained Liquid of neutral reaction.

If acetyl chloride is used instead of benzoyl chloride, one also obtains a water-soluble liquid of neutral reaction.

Ha. 262 parts of dipropylenetriamine (2 mol) are mixed with 380 parts (4 mol + 10% excess) of butyrolactone with stirring. The temperature is brought to 200 to 23O ⁰ C, held for 3 hours at 23O ⁰ C and finally increased 2 hours at 25O ⁰ C. After volatile constituents have been distilled off in vacuo at 5 mm to 155 ^° C., 517 parts of a water-soluble, brownish-colored, viscous liquid with a strongly basic reaction remain.

lib. If one uses - as described in the example Ha - Instead of 262 parts of dipropylenetriamine, 290 parts of N-methyjdipropylenetriamine (2 moles) or 318 parts of N-ethyldipropylenetriamine (2 mol) under otherwise identical conditions, one also obtains clearly water-soluble, viscous, brownish colored liquids which are the corresponding N-alkyl derivatives.

III. 380 parts of butyrolactone (4 moles + 10% excess) are mixed with 292 parts of triethylenetetramine (2 moles) and heated with stirring to 230 ⁰ C, held for 3 hours at this temperature and finally heated for 2 hours at 25O ⁰ C. After volatile constituents have been distilled off, finally in a vacuum of 5 mm to 130 ° C., 557 g of the product, which is clearly soluble in water, are obtained.

IV. If one uses in the regulations I, Ha, Hb and III instead of 380 parts of butyrolactone 440 parts of valerolactone (4 mol + 10% excess) or 496 parts of γ-ethylbutyrolactone and works under otherwise identical conditions, one also obtains clear water-soluble, resin-like ones Products containing the corresponding dipiperidone compounds or by ethyl am Pyrrolidone ring substituted compounds are:

CH ₂

H ₂ C

H ₂ C.

CH ₂

CO

H ₃ C

CH ₂

respectively.

H ₅ C ₂ - HC

CO

Va. 264 parts of di (γ-aminopropyl) ether (2 mol) are heated to 70 ° C. and mixed with 380 parts of butyrolactone (4.4 mol) while stirring. After the decay of the heating is heated first for 2 hours at 120 ⁰ C and then again hours at 240 ° C, the reaction water distilled off. In a vacuum of 5 mm Hg, the excess butyrolactone and the remaining water of reaction are completely distilled off within 1 hour. 520 parts of a brownish, highly viscous residue are obtained, which is clearly soluble in water and reacts neutrally:

L-CH ₂ -CH ₂ -Ch ₂ -O-CH ₂ -CH ₂ -CH ₂ -L

L = —n:

, Cfio - CHo

CO — CH,

Vb If 263 parts of 1,2,3-tri- (γ-aminopropoxy) propane are heated (1 mol) and 290 parts of butyrolactone (3.3 mol) under the same, under Vabeschritten-

NEN conditions, 450 parts of crude 1,2,3-tri- (y-pyrrolidylpropoxy) propane are obtained as residue, which is a clear, water-soluble, highly viscous oil:

O £ 1.2 'CH ₂ CH ₂ ' L

L - CH ₂ - CH ₂ - CH ₂ - 0 - CH ₂ - CH - CH ₂ - O - CH ₂ - CH ₂ - CH ₂ - L

VI. 240 parts of sodium sulfide containing water of _{crystallization (Na 2 S -9H 2} O) (1 mol), dissolved in 400 parts of ethanol, are heated to the boil. 295 parts of S-chloroethylpyrrolidone (2 mol), dissolved in 200 parts of ethanol, are added dropwise and the mixture is refluxed for 3 hours. The solvent is then evaporated. 380 parts of a clearly soluble residue are obtained which, in addition to sodium chloride, contains the sulfur-containing dipyrrolidone derivative.

VII. In 6O ⁰ C is slowly 424 parts of acrylonitrile a polymerization inhibitor dropwise with stirring in 131 parts of diethylenetriamine (1 mole) (8 mol) in the presence of and then holding the reaction mixture for 7 hours at this temperature. The excess acrylonitrile is removed in vacuo at 12 mm Hg by distillation at 5O ⁰ C. The residue obtained (454 parts) is hydrogenated in 1000 parts of methanol saturated with ammonia in the presence of 70 parts of moist Raney cobalt at 100 ^° C. and 200 atm. Hydrogen until the calculated amount of hydrogen (10 mol) is absorbed. The catalyst is filtered off, the solvent is evaporated off in vacuo and the residue (460 parts), which is pentaaminopropyl-dipropylenetriamine, is reacted with 475 parts of butyrolactone (5.5 mol) under the conditions described under Va. A dark, tough resin is obtained which is easily and clearly soluble in water.

The parts mentioned in the examples are parts by weight.

example 1

A blind vat is set up which contains 5 g of sodium dithionite and 12 cm ^{3 of} 38 ° Be sodium hydroxide solution per liter. Be in this vat

a) without further addition,

b) with the addition of 5 g / l N-methylpyrrolidone (= Leveling agent according to patent 818 042),

c) with the addition of 0.3 g / l of the condensation product of 2 moles of butyrolactone and 1 mole of diethylenetriamine,

d) with the addition of 1 g / l of the agent mentioned under c),

e) with the addition of 5 g / l of the agent mentioned under c),

f) with the addition of 1 g / l of a 30% strength aqueous Solution of polyvinylpyrrolidone (according to patent 843 400),

g) with the addition of 3 g / l of the agent mentioned under f),

h) with the addition of 15 g / 1 of the agent mentioned under f)

one non-colored and one using the usual IN method (with 2% of the coloring matter of the constitution

With 2% of the coloring matter of the constitution

, C ₂ H ₁ OH

-N = N-

■ n;

dyed textile material made of acetate grayon is combined with the same, but undyed Material treated without any additives for 1 hour in a bath at 75 ° C. at a liquor ratio of 1:30. The initially uncolored material is hardly colored. On the other hand, if the liquor is exposed to 12 g / l of des Moltriethylenetetramine and 2 moles of butyrolactone dilactams obtained, so finds already after very A short time the equilibrium of the dye takes place.

If the leveling agent described is replaced by the compounds obtainable according to I or Ha to Hb, a similar effect is observed. The differences in the effect of each product are not very large and otherwise due to the dye.

Example 2

The superior effect of the agents used according to this invention is evident from the following comparative tests emerged.

Dyed cotton strand treated together for 45 minutes at 60 ° C. in a liquor ratio of 1:30. While this treatment balances the dye between the dyed and undyed cotton strand instead of. The degree of compensation, i.e. H. the uniformity of the shades after treating the cotton strands, is a measure of the effect of the leveling agent used.

The comparison of the rinsed, oxidized and normal in the blind vat after the treatment finished cotton strands shows that the same leveling effect took place in samples c) and d) has, as in sample b), although in sample b) a multiple of a known agent is used has been. Sample f) shows a certain coloration of the original material, but it is clearly weaker is than that of samples c), d) and also b). If one now increases the concentration of the aid in f) - Samples g) and h) -, the balancing effect is in no way increased; due to the very strong retarding effect of the agent in samples f) to h), the originally uncolored material remains almost colorless dyed strands are very clearly lightened and the residual dye is retained in the dyebath. Sample e), in which the same amount of leveling agent was used as in sample b), proves this

7 8

The top effect of the diering effect used according to the invention results in a level, well-colored one Product. and strikingly calm tint.

Example 3 If one uses the one made according to HI and with

Ethylene chloride or dichlorodiethyl ether reacted

On the mechanical yarn dyeing machine (after 5 products, you also get excellent we-tanners) are rayon yarns after the IN-Verkungen.

run in a liquor ratio of 1:30 with 2% INDAN- Example 6

THREN brilliant green B PIv. fine high conc. f. col.

(C.I. 59825/1956) dyed, the dyebath having a one with 2% INDANTHREN blue green FFB PIv.

Addition of 1g / 1 of the fine f. Color produced _{according to I 3 paragraph 1.} (CI 70305/1956) dyed cotton product is obtained. yarn is mixed with equal amounts of undyed

The dye pulls slowly and evenly on like yarn on a winding dye bath after which the fiber. The dyebath is foam-free and the IN process yarns in a liquor ratio of 1:30 ³ / i hours do not float. The final fleet contains ratio treated. It should be achieved that after the moderately little dye. After the usual treatment, the yarns are both yarns the same shade and the finish is equal and well dyed. If you have the same depth of color (equalization), without the addition of the dyeing agent, if you do not use any agent for winding the dye bath, then

Dye on so quickly that the color is uneven. the compensation is very low. When adding well-used one surface-active leveling agent th leveling agents, e.g. B. 2 g / l of the oxethylated Octavom The type of oxethylated fatty alcohol or fatty decyl alcohol (molar ratio 20; 1) is the balance amine or quaternary surface-active ammonium relatively good, but the depth of color of the colorations compounds, level dyeing is still obtained - little and the loss of dye in the dyebath is large, gen, but there is too much dye in the remaining liquor, when adding 0.5 g / l of the oxethylated octadecyl

and the dye tape foams so that the yarns on the amines (molar ratio 7: 1), which is subsequently added with Di-liquor start swimming. As a result, the 25 methyl sulfate was peralkylated, which is also a mechanical one Moving is prevented and the dyeing is uncertainly compensated, but the color tone is after made possible. Turned blue, on the original one

In place of the above-mentioned well-suited equal-white yarn, it is strongest, and is also the dye-sizing agent the two according to I are also suitable, loss in the dyebath due to the retarding effect of the Paragraphs 2 and 3, resources available. They make a big difference of 30 tools.

differs from the former in that their retarding- When adding 5 g / l of methylpyrrolidone or capro-

effect is even less. The lactams or the reaction product of pyridine are also suitable according to Va) and b) available di- or tripyrrolidone with chloroacetic acid is a significantly better compensation compounds that can be determined as a heteroatom between the as without addition.

Lactam rings have oxygen atoms, and the ethyl- 35 The equally good result can be achieved with only 1 g / l of the im pyrrolidone derivative according to IV. Example 1 or the products mentioned in Example 3

. be achieved. If you use 5 g / l of these products,

Example 4 _{SQ ore} j _e i _{to e} j _{t nen na} hezu rest without compensation, wherein

On a closed dyeing machine (after no color changes occur, and the color Obermeier), cheeses or warp beams are made from cotton by the retarding effect that is relatively low according to the IN process in the liquor is low.
ratio 1:10 with 1% INDANTHREN-Blue BC example 7

PIv. fine f. col. (C.I. 69825/1956) colored. Otherwise

The usual way of working is used as the only leveling agent.

2 g / l of the product made according to Ha, the piece of wool to be dyed with vat dyes after the pad bath admitted. After the usual completion, the steam processes are 5 to 20 g / l of the reaction product colored bobbins with good levelness of pure, symmetrical dichlorodiethylthioether with pyrklarer Nuance and perfect uniformity rolidon (see regulation VI) or the color made from it. Only a little dye remains in the dye bath when sulfoxides or sulfons are added return. 50 one with a high dye yield a substantial

In the same way as the product made according to Ha - more equal and better through-dyed goods than without it Its conversion additives are used as leveling agents.

products with ethylene chloride, dichlorodimethyl ether, example 8

Succinic acid dichloride and that obtainable according to VII

Connection suitable. For these products, the 55 Retarding effect even less than with the first IMMEDIAL-Indonviolett B extra (C.I. 53440) im mentioned. Liquor ratio 1:30 at 95 ° C with 8% soda, 60%

Example 5 Sodium sulfur, 50% Glauber's salt IV ge for _{2 hours}

colors. The color tends to bronzing, is rubbing

On an automatic jigger, cotton becomes fake and uneven. A flawless coloring will be raincoat poplin colored, this is achieved by adding 1 g / l of the prepared according to I beforehand on the foulard with 1% INDANTHREN-Oliv T PIv. Product, fine f. col. (C.I. 69525/1956) padded fabrics in example 9

Liquor ratio 1: 5 on the jigger after the IN-

Process developed. The developing bath gets 65. On the reel skid, tricot is made of viscose rayon in addition to the usual additions of hydrosulfite, lye with 0.2% Chicago blue 6 B (CI. 24410/1956) and padding liquor no additives other than 2 g / l of the normal dyeing process; the color falls according to III manufactured product. With low retar- unequal from. But if you add 0.5 to

g / l of a product mentioned in paragraph 2 of example 4, the color is obtained with otherwise the same procedure flawlessly does not matter. The same successes are achieved with the products according to II b and IV.

Claims (2)

PATENT CLAIMS: 1. Use of compounds with two or more lactam residues in the molecule, which are caused by Carbon chains are linked together, which carbon chains are connected by at least one Oxygen atom, by a sulfoxide or sulfone group or by an optionally by a An alkyl group with not more than 3 carbon atoms, an aliphatic acyl group with not more than 3 carbon atoms or by one aromatic acyl group substituted imino group are interrupted as leveling agents in textile dyeing. 2. Use of such compounds according to claim 1, by reacting at least two at least two lactam residues and at least one - NH group-containing molecules with at most 5 carbon atoms containing dihaloparaffins or aliphatic dicarboxylic acids or their derivatives have been obtained as leveling agents in textile dyeing. Considered publications:
German Patent Nos. 818 042, 843 400, 154, 955 409;
British Patent No. 735 396. 209 627/294 7.