DE2334655B2 - COMPOUNDS CONTAINING AZIRIDINE RESIDUES AND THEIR USE TO REDUCE THE RUNNING AND FELTING OF PROTEIN FIBERS, OR GOODS - Google Patents

Description

For example by St. B. S e 1 1 ο and G. C. T e s ο r ο. Applied Polymer Symposium No. 18, 629 (1971) are reaction products of polyalkylene Oxides with diisocyanates and ethylene imine are known as wool finishes. However, they are difficult emulsifiable and have a strong tendency to form a very annoying sticky coating on the foulard rollers do form.

From the German patent specification 12 65 114 it is known the shrinkage and matting of fibers, threads, yarns and fabrics made of wool and silk as a result tu lessen the materials with solutions containing 1 to 10% of a water-soluble aziridine compound the general formula

A-

-CH - N

also - but recommended in a very general way for changing the properties of wool.

After knowing this in the mentioned writings

taught doctrine one had to assume that keratin fibers Basically, the 2 or 3 aziridine rings can be equipped with any kind of low-felt connection contain as functional groups and through which a crosslinking of the peptide chains of the keratin fibers he follows. An influence of the type and the molecular weight of group A of the above formula on the According to the state of the art, the effectiveness of the product was not to be expected.

It must therefore be surprising to find some special products among the bifunctional aminoaziridines with a very specific molecular weight range have been found, which are conspicuous with regard to highlight their effectiveness for the anti-felting finishing of keratin fibers. These highly effective Products are not mentioned in the publications mentioned. These novel substances correspond to the general formula

contain, soaked, then dried and reacted with the aziridine compound, where in the uncommon formula η 2 or 3, R ₁ -R ₂ and R ₃ hydrogen atoms or lower alkyl radicals, R ₄ hydrogen, a lower alkyl radical or an OH group and A. an n-valent radical from the group! per alkylenes bound to the rest of the molecule through C - C bonds. Aralkylenes. Oxalkylcne. Hydroxyl Isubtkiluiertcn alkylenes, SO ₂ -containing alkylenes, a carboxylic acid ester radical and a conjugated double bond radical.

In the French patent 1 5 44 210 are Among a larger number of esters from alcohols and iridincarboxylic acids, there are also some • whose polyol components are made from polypropylene

(Glycols with molecular weights of up to 20,000 are: the entire class of substances is among others

R ₁

1 ^x

Q-r-X-C-C-C-N

R ₄ R ₂

R-

in which R ₁ to R, hydrogen atoms or low molecular weight alkyl radicals. Q is the remainder of an n-valent alcohol or phenol with a molecular weight of h2 to 300.η 2 or 3, X is a polyether chain of butowiind (propow and optionally ethoxy units with an atomic ratio C: O of at least 2.67: 1 and a molecular weight \ on 150 to 1500 at η 2 and from 150 to 3000 at / 1 3 means.

ί-L

Examples of low molecular weight alkyl radicals are those with 1 to 3 carbon atoms, such as, in particular, methyl, are suitable; but are preferred those substances of the formula I which have hydrogen atoms as radicals R to R. '

It has also been found that a method of reducing shrinkage and Entangling of protein fiber-containing or consisting of material by impregnation with a Equipment bath containing at least one compound with several azidine residues, and implementation of the Azidine residues with the protein avoid the disadvantages mentioned and get better than the previous results can be achieved if the compound containing azidine radicals is at least one substance of the formula 1 used.

The substances of the formula I can be prepared by processes known per se, for example by contacting an n-valent alcohol or an n-valent phenol of the formula

0 (H) _n ""

in which H is a hydrogen atom bonded to oxygen, one or more alkylene oxides and or tetrahydrofuran to a polyether of the formula

O-fX-H) "" Π,

- or by adding a polyether of the formula IH by polymerizing tetrahydrofuran andor one or more alkylene oxides, so that the entire molecule cruppc —X— Q— X— possibly from a uniform Polyether consists - and with this Polyäthcr an i-aziridinocarboxylic acid ester of the formula

(IV)

O R, R, \ R < / il RO-C- -C-C-N R- R ₄ R ₃

«-Fold transesterified. In this formula, R denotes a low molecular weight alkyl radical. preferably the methyl radical. Q and X in formulas II and _{III and R 1} to R ₇ in formula IV have the meaning given above for formula I.

N-valent alcohols or phenols are those with a molecular weight of 62 to 300 into consideration. These can be aliphatic. cycloaliphatic or aromatic polyalcohols to mono- or polynuclear polyphenols or substances with phenolic and alcoholic hydroxyl groups Act. Examples are:

Aihvlenglycol.

I.2 propylene glycol.

l.3-l'ropylcng! \ col.

Bui \ lcngl> kolc.

Ilexanediol.

Diet Lulene Glycol.

Dipropslenghkole.

[) ih \ dro \ vdibut \ lather.

Glycerin.

Hydroquinone.

Resorcinol,

Catechol,

4,4'-dihydroxydiphenyl.

2,2-bis- (4-hydroxy phenyl! Propane.

Pyrogallol,

Phloroglucine,

Saligenin.

The selection of the type and amount of the substances to be added to the substances of the formula II or those to be polymerized Components as well as those of the addition or polymerization conditions are encountered in in a manner known per se in such a way that the chains X have the desired average molecular weight and an atomic ratio from carbon to oxygen of at least 2.67: 1. The chains X can therefore from pure butoxy or propoxy units. they can also contain both butoxy and propoxy units contain; In addition to these units, they can also contain as many ethoxy units contain that the said atomic ratio is not exceeded. Polyether chains that only consist of Ethoxy units are built up have an atomic ratio C: O as 2: 1 and are therefore not suitable for the present invention.

In the case of substances of the formula I with η = 2, the molecular weight of the polyether group X is in the range from 150 to 1500, preferably from 200 to 1250; at η = 3 it is 150 to 3000, preferably 200 to 2200.

At η = 2 they have a pronounced optimum effect when the molecular weight of the —X —Q — X— group is around 2000. If there are deviations from this, the effectiveness decreases continuously on both sides. In the case of substances with η = 3, the optimum mine is so clearly pronounced.

For the effectiveness of the substances of the formula I, it is not of essential importance how different Alkoxy units in the chains X are distributed. Accordingly, the alkoxy units can, for example are in the form of interconnected blocks (cf. the schematic formulas V to X); But they can also be distributed statistically over the chains (cf. the schematic formulas Xl to XIV); Finally, mixed forms of these two extremes are also possible (see the schematic formula XV):

t tFOl ,,

\ a ■ (BO)!

\ h (PO)!

in (BO) i
\ b (HO)!

IVl)

(VIII

(VMlI

ilXi
l. \ l

iXH
(XlIl

a- (PO) I_
b ■ (EO) J

α (BOjI
b · (PO) | c ■ (EO))

P ' ^(PO) l-

^. . _{E0) j

(XIII)

(XlV)

(XV)

BO = butoxy, PO = propoxy, EO = ethoxy radicals. two little each.

The indices used in formulas V to XV a. b and c represent positive numbers which are selected so that the above conditions for molecular weight and carbon-oxygen ratio are met.

The substances of the formula III obtained by polyaddition or polymerization are known not to be uniform substances, but rather mixtures of substances of different chain lengths which are referred to in English as “cogene mixtures”. The information on molecular weights and atomic ratios are therefore to be understood as mean values.

/ i-Aziridinocarboxylic acid esters of the formula IV are known or if they have not yet been described - by methods known per se / jagially. for example by implementing acrylic. Methacrylic or crotonic acid esters or of, i-chlorocarboxylic acid esters with aziridines.

The substances represented by the general formula I are incomplete or incomplete at room temperature soluble in water. You can be in water preferably with nonionic or cationic Convert emulsifiers into finely dispersed, very stable emulsions or dispersions.

Depending on the nature of the radical Q, the substances of the formula I are Liquid or solid at room temperature. In particular with solid products, this has been proven Mixing with anhydrous auxiliaries such as emulsifiers, wetting agents, anti-migration agents or Softeners to bring them into a liquid consistency at room temperature. Due to the functional Selection of these tools can be achieved that the Production of the emulsions by pouring water into the liquid product mixture without additional use of emulsifiers can take place.

To prepare the equipment fiot, a stock emulsion can first be prepared by add the same amount of cold water to the product while stirring mechanically. Depending on the type of used Emulsifiers or auxiliaries, this emulsion can initially take on a paslenike consistency, which, however, becomes thin and pourable after adding more water. This tribal emulsion the AusriisHingsfiottc added. If necessary, a non-ionogenic or cationic wetting agent is added and the Adjusted the pH of the bath.

The stability of the aqueous dispersions or emulsions of the substances of formula 1 depends on among other things on the pH value. If their pH value is below 4. the azidine rings are dependent on the Degree of dispersion usually split so quickly that the effectiveness of the products quickly declines. in the

The stability of the 2.5 to 5% product contained is in the pH range from 5 to 10, preferably from 5 to 7 Tending aqueous preparations, however, generally «at least 12 hours, one door the concerns of the practice: sufficient resistance.

The limited shelf life of the substances of the formula in the presence of water means that this « Products must be stored in an anhydrous state in order to be effective over a period of time of at least 6 months.

The emulsions or dispersions from Steffel of the formula 1 can be nad without difficulty usual methods on protein fibers containing: or goods consisting thereof, e.g. B. on fibers. Threads Top. Applying yarns as well as woven and knitted goods made of wool or silk. The permanent one Fixation of the products on the polypeptide-containing substrate can, after drying, preferably he Temperatures up to J 50 "C and pH values from 5 to H take place. If the protein fibers are sufficiently reactive, the fixation reactions must be carried out no catalysts required.

The reactivity of the protein fibers depends untci other things depend on their pretreatment. It has mcIi z. B. found that a pretreatment do Goods to be equipped with aqueous liquor at increased Temperature increases the reactivity of the protein fibers so that catalysts can be dispensed with Such a pretreatment is, for example, the dyeing of the goods before finishing.

If the reactivity of the protein fibers to be treated turns out to be too low, the implementation can take place with the aziridine residues are supported by catalysts. As such come for example Metal salts are considered, as they are also used as acetalization catalysts are common in the reaction of cellulose with N-methyl groups; called be zinc nitrate. Magnesium chloride and especially zinc sulfate. It is convenient to use these catalysts to apply the equipment to the goods before impregnating them with the equipment. Free acids, e.g. B. Sulfuric acid, act catalytically in the desired sense, if you have previously applied it to the equipment Applies well; however, they have the disadvantage. that they adjust the pH of the equipment that is located in the impregnation device, lower and thus affect their durability.

Another way to support the reaction between the protein fibers and the aziridine residues, consists in the finishing bath in addition to at least one substance of formula I and optionally the other above-mentioned auxiliaries one or more low molecular weight, at least 2 N-methylol and / or substances containing N-methylol ether groups, at least one acetalization catalyst and adding a dispersion of at least one film-forming acrylic ester polymer.

Substances containing low molecular weight N-methylol and / or N-methylol ether groups are generally known and used as finishing agents for cellulose fibers. These are preferably substances with a molecular weight of up to 350, which _{contain two or more groups of the formula CH 2} - OR bonded to nitrogen, in particular to the nitrogen of a carbamide group, in which R is a hydrogen atom or a low molecular weight alkyl radical preferably 1 to Is 4 carbon atoms. Particularly preferred studs of this type are

those of the general formulas

Il c

R ₂ O-CH ₂ -N N-CH ₂ -OR ₁

j i

(XVl l

R ₄

R,

I!

R ₁₀ O-CH ₂ -N 0-A-

-O-C-N CH

OR ₁ , OR

(XVIl)

crhighlighted. wherein R ₁ and R _{2 are} hydrogen atoms of the low molecular weight alkyl groups. R, and R ₄ radicals in the formula

R ₁ .
the immediate or over

R-
-C— -O-

- N -

are connected to one another, or hydrogen atoms, low molecular weight alkyl groups or low molecular weight alkoxymethyl groups. R ₅ , R .. R ₁₀ and R _{11 are} hydrogen atoms or low molecular weight alkyl groups. R _n and R _s hydrogen atoms. Hydroxyl groups, low molecular weight alkyl groups or low molecular weight alkoxyl groups. R _{9 is} a low molecular weight alkyl group or a low molecular weight hydroxyalkyl group, R ₁ and R _{13 are} hydrogen atoms. low molecular weight alkyl groups or low molecular weight alkoxymethyl groups, A is a divalent aliphatic hydrocarbon radical having 2 to 8 carbon atoms and Z is zero or 1. The radicals R ₁ to R ₈ and R ₁₀ to R _{13 defined together} can be identical or different. Preferred low molecular weight alkyl, hydroxyalkyl, alkoxyl and alkoxymethyl groups are those which! contain up to 4 carbon atoms in the alkyl part.

Examples of substances of the formula XVl include: derivatives of urea. Monoalkyl and symmetrical dialkyl ureas containing at least 2 hydroxymethyl groups or low molecular weight Contain alkoxymethyl groups, such as N.N -dihydroxy methy lurea. N.N-dimethoxymethyl urea. ' N.N - dibutoxy methyl - N - methy! Urea.

N.N'.N'-trimethoxymethyl-N -ethylurea and N.N'-diethoxymethyl-N.N'-dimethylurea. the N.N-dihydroxymethyl derivatives and low molecular weight N.N'-dialkoxymethyl derivatives of N.N'-Athy-

: s lenurea (= imidazolidone-2). N.N "-1.2 propylene urea (= 4 - methylimidazolidone - 2), N.N '1.3 - propylene urea (= N.N' - trimethylene urea or hexahydropyrimidone-2), 5-hydroxyhexahydropyrimidone-2, 4-hydroxy and 4-alkoxy

V) 5,5-dialkylhexahydropyrimidones with low molecular weight Alkyl and alkoxyl groups, hexahydro-1,3,5-triazinon-2 and its 5-alkyl and 5-hydroxyalk \ lderivatives. Glyoxalmonourein (= 4,5-Dih'ydroxyimidazolidon-2 and Uronen.

Examples of substances of the formula XVIl are the hydroxymethyl derivatives and the low molecular weight ones Alkoxymethyl derivatives of the mono- and dicarbamic acid esters (= mono- and diurethanes). such as ethyl carbamic acid (Urethane in the narrower sense). Propyl, butyl and octyl carbamic acid. N-methylcarbamic acid ethyl ester. N-ethylcarbamic acid butyl ester, dicarbamic acid ester and di-N-ethyicarbamic acid ester of ethylene glycol. 1,3-, 1,4-butanediol and 1,6-hexanediol.

In addition, however, other low molecular weight compounds are also suitable for the present process. N-methylol and / or substances containing N-methylol ether groups, for example optionally etherified N-methylol compounds of aminotriazines.

> o like melamine. Ammeline and Ammelid, from guanidine. Dicyandiamide and dicyandiamide ^, thiourea and acetylenediurea (= glyoxaldiurein).

In general it can be said that the type of low molecular weight N-methylol and / or substance containing N-methylol ether groups is not an essential feature of the invention.

The low molecular weight, N-methylol and / or N-methylol ether groups containing substances are hereinafter referred to as "aminoplasts" for the sake of simplicity.

Acetalization catalysts are used in the finishing of fiber material with finishing agents in general applied. They are usually somewhat imprecisely referred to as curing catalysts. It deals are preferably latently acidic salts, d. H. Salts that are not or only slightly acidic by themselves, but release so much acid by hydrolysis or thermal influence that the reaction between

609 542/473

the fiber guide and the equipment accelerated will. Latent acid salts are mainly salts from ammonia. Amines or polyvalent metals and medium-strength or preferably strong acids, for example ammonium chloride, ammonium sulfal, * Ammonium phosphate, ammonium nitrate, di-monoethanolammonium hydrogen phosphate, ethanolammonium chloride, 1 - Hydroxy - 2 - methy lpropy lanimonium-2-chloride. Magnesium chloride, aluminum chloride, zinc chloride, zinc nitrate. Zinc sulfate and zirconyl chloride. The catalyst is chosen in the usual way in accordance with the intended working conditions the end. In some cases it is advantageous not to use individual substances but rather mixtures of several substances to use as catalysts. Strong or medium-strength inorganic acids, such as hydrochloric acid, Sulfuric acid, phosphoric acid, oxalic acid. Glycolic acid. Maleic acid, monochloroacetic acid. Trichloroacetic acid. Tartaric acid and citric acid have a catalytic effect in the desired sense, but apply for their applicability the same restrictions as above for their use for catalysis of Reaction between protein fibers and aziridine residues indicated.

Dispersions of film-forming acrylic ester polymers; _s are generally known and widespread as aids in the finishing of textile fibers. For the Purposes of the present invention come into consideration above all those polymers which, in addition to the Acrylic ester units responsible for the film-forming properties and possibly units of others olefinically unsaturated monomers contain polymerized groups that can be mixed in, for example Unetherified or etherified N-methylolacr \ l and methacrylamide groups and epoxy or halohydrin groups. Such dispersions of film-forming Acrvlesterpoiyrnerisate z. B. in German Aus'legeschnften 10 47431, 11 10606, 1209989. 1494871, German patent specification 1140 898 and US patents 27 19 072, 27 80 608. 30 78 185 and 31 00 674.

The concentration of the equipment bath on the components discussed depends on itself known manner according to the impregnation devices used and the desired liquor pick-up. It is chosen so that the following quantities of the components are applied to the goods to be equipped: Substances of the formula I 1 to 5%, emulsifier 0 to 1%. Aminoplasts 0 to 2%, acetalization catalysts 0 to 0.5%, film-forming acrylic ester polymers 0 to 4% (all percentages based on the weight of the dry fiber material).

The finishing of textile fabrics containing or consisting of protein fibers against matting and shrinking during machine washing is very simple in terms of process technology. B. padded with the equipment in the usual way and dried and fixed in one operation on the needle frame at temperatures of 100 to 150 ⁰ C, preferably at 110 to 130 ^c , including 1 to 10 minutes, preferably I ¹ I ₂ to 2V ₂ minutes are required. The fixing conditions, for which examples are given, depend on the construction and the basis weight of the goods and on the technical requirements of the machine.

The merging of drying and fixing has proven particularly useful in the finishing of Knitwear proven! To tension deformation of the warp-sensitive goods before fixing to avoid.

If you dry the padded with the equipment Goods in the temperature range from 60 to SO C. This is how the aziridines react with the polypeptides of the goods to be equipped has not yet taken place. Goods sensitized in this way can be used in condensation machines or fixed with shaping on ironing presses.

The finished product containing or consisting of protein fibers is permanently against the Matting and shrinking in mechanical washing machines and in drum dryers (e.g. tumblers) protected. The temperature of the wash liquor should preferably be 40 ° C .; it can with something lower Requirements for dimensional stability can be increased up to 60 C.

When finishing materials made of protein fibers that have been pre-dyed with acid or reactive dyes the substances of the formula I increase the general fastness properties of the dyeing not or only slightly impaired in exceptional cases. The same applies to the authenticity of dyes on partly processed synthetic fibers based on polyethylene terephthalate. Nylon 6.6. Nylon 6 and polyacrylonitrile.

Dyeings with direct and reactive dyes on cellulose fibers can be carried out using substances of the formula I. may be impaired in the lightfastness, but will In comparison, protein fibers are only slightly mixed with cellulose fibers.

Materials made from protein fibers can also be used after finishing with the substances of the formula I in are usually dyed with acid and reactive dyes. The speed of absorption of the dyes is increased by the equipment products in many cases. This way of working has the advantage that the dyeing of already finished goods on reel runners or other particularly economical working dyeing machines can be carried out without the risk of the goods being melted.

In a particularly preferred embodiment of the method according to the invention, which are above all has proven itself in fiber material containing keratin. one proceeds in such a way that one can facilitate the implementation of the Azindine residues with the protein the goods to be treated before or during the impregnation with the equipment bath treated in a manner known per se with a solution which is an inorganic or organic Contains the salt of sulphurous acid, and the goods so treated with the salts of sulphurous acid Lets acid react.

Examples of salts of sulphurous acid are: sodium sulfite, sodium hydrogen sulfite Sodium disulfite, ammonium hydrogen sulfite. 1 nathanolammonium hydrogen sulfite.

This process variant can therefore be carried out in two baths or in one bath.

In the two bath Verfahrensführune by first soaking the product nit an aqueous solution of a sulphite salt, preferably in the pH range ^v ° ^{n 4,} R ^{1 S 5} · In this case, it has proven useful to measure the amount of sulphite salt so that 1 to 3 %

fj ^{gen on the} dry weight of the goods available to them. The goods treated in this way are then either celaeert or rolled wet at normal temperature for 24 to 48 hours.

dries and heated or heated when wet. The heating can be carried out in the usual way with contact heat, depending on the moisture content of the goods. Radiant heat, can be stirred with hot air or steam. It has proven itself that -. Bring the temperature of the goods to at least 100 C; they are preferably heated to KK) up to 130 C. Heating times of 2 to 5 minutes are sufficient. The item treated in this way can then be impregnated with the finishing bath as explained above. which contains the substance of formula 1 and, as also explained above, treat it. Keratin-containing fibers are activated by pretreatment with sulfuric acid salt in such a way that they react with the substances of formula 1 at normal temperature; goods of this type that have been impregnated with a finishing bath therefore only need to be left to their own devices at normal temperature for 30 to 120 minutes in order to allow the reaction to proceed. This is done expediently by winding up the m impregnated and squeezed-off goods and holding the roll horizontally in rotating motion the entire time. The substances of formula 1 can also act from a long liquor on the material pretreated with sulphurous acid salts. : s by moving it for 45 to 60 minutes in an aqueous bath containing substances of formula 1. Another possible variant is that drying the pre-treated with sulphite salts and impregnated with the finishing bath Good v> immediately at any temperature, since the reaction between the protein and the substances of formula 1 is not bound to the presence of water. Finally, it is also possible to remove the substances of the formula I from organic solvents, for example from chlorinated hydrocarbons. to be applied: these then only need to be evaporated and the equipment is ready.

In the single-bath mode of operation, the goods to be treated are treated with sulphurous acid salt and with substances of Formula 1 at the same time. Since sulfurous acid salts, like all electrolysis, can impair the stability of emulsions in general, i.e. also of emulsions of the substances of the formula I, care should be taken when combining the two components. In particular, it should be ensured that the finishing _{bath does not contain more than 15 g / l SO 2} as sulfurous acid salt and not more than 50 g / l substance of formula 1. In addition, it has proven useful to predilute the aqueous solution of the sulphurous acid salt as extensively as possible and to stir the abovementioned stock emulsion of the substance of formula 1 into this for the preparation of the finishing bath. Furthermore, in the interest of sufficient stability of the finishing bath, care should be taken that its pH value does not fall below 5.5. It has also proven particularly useful in this single-bath process, in which sulfite and aziridine compounds are together in the equipment liquor, to use compounds of formula 1 whose group X has a molecular weight of at least 600, preferably more than 700. if η = 2, and at least 400, preferably over 500. if /! = 3, and in which (regardless of the size of n) the atomic ratio C: O of X is at least 3.

The item to be equipped is impregnated with the bath prepared in this way, and then as above for the first one Stage of the two-bath mode of operation explained stored at ordinary temperature or dry odei heated wet. The impregnated goods have also proven to be particularly effective at first at temperature! to dry at 100 ° C and then steam them at 10 ° C for 5 minutes.

The one or two bath use of sulphurous acid salts in the Ver according to the invention Driving enables a particularly fiber-friendly implementation, as only moderate temperatures are required that will not harm proletarians.

The aziridine derivatives A to M and W to Z used in the examples were by transesterification of Di or triols with / f-aziridinopropionsäuremethvleste won. They correspond to the following formulas

A. CH ₁ -CH, -CH, -CH, -O -

1 * ο

CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-

B. CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-

CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-

C. H ₃ C-CH-O-

HCH ₂ —CH, —CH, —CH, —O) ₆ —CO — CH, —CH ₂ —N

-4CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) ₁₃ -CO-Ch ₂ -CH ₂ -N

CH,;

CH ₂ CH,

CH ₃

CH ₂ -O

D. H ₃ C-CH-ΟΙ
CH, -Ο -

CH,

- (C ₂ H ₃ (CH ₃ ) - O) - - CO CH ₂ - CH ₂ - N CH,

- (C ₂ H ₃ (CH ₃ ) -Ο-) ₁₇ CO-CH ₂ -CH ₂ -N

CH,

CH,

13th

14th

Οι

E. H ₃ CC-CH.,

HC ₂ H ₃ (CH,) - Ο-I ₄ CO-CH ₂ -CH ₂ - N

CH,

CH,

Ο—

F. CH ₂ -O CH - Ο— CH ₂ -O

Ci. CH, -ΟCH - Ο—

HC ₂ H ₃ (CH ₃ ) -Of ₂ HCH ₂ --CH ₂ -O) ₅ -COCH ₂ -

HC ₂ H ₁ (CH ₁ I-Ot ₂ HCH ₂ -CH ₂ Oi _1n -CO-CH ₂ -CH ₂ -N

CH, -Ο - CH ₂ -O-

CH-Ο -

HC ₂ H ₃ (CH ₁ I-OfHCH ₂ -CH ₂ -O) ₅ -CO-CH ₂ -CH ₂ -N

CH ₂ -OJ. (CH ₂ I ₄ -Ο - O

(CH ₂ I ₄ -Ο - K. (CH ₂ I ₄ -Ο - O

(CH ₂ I ₄ -OL- (CH ₂ I ₄ -O-

CH,

⁽ Ί CH ₂ J,

CH,

CH, j, CH, '

CH ₂ 3

IHCH ₂ -CH ₂ -CH ₂ -CH ₂ -Ot ₁ TtCH ₂ -CH ₂ -Ol ₅ -COCH ₂ -CH ₂ -N

HCH, -CH ₂ -CH ₂ -CH ₂ -O) ₁₁ - (CH ₂ -CH; -O) ₅ -COCH ₂ -CH ₂ -N

HCH ₂ -CH ₂ -CH ₂ -CH ₂ -OtHCH ₂ -CH ₂ -Ot ₁ -CO-CM ₂ --CH ₂ -N

(CH ₂ I ₄ -O-

M. H ₃ C-CH-O-CH ₂ -O-

W. H ₃ C-CH-O-CH ₇ -O-

HC ₂ H ₃ (CH ₃ I-OtTHCH ₂ -CH ₂ -O) ₅ -CO-CH ₂ -CH ₂ -N '

HC ₂ H ₃ (CH ₃ I-OtTHCH ₂ -CH ₂ -O) ₁₀ -CO-CH ₂ -CH ₂ -N

CH ₂

CH,,

Vh,

X. CH ₂ -O-CH, -Ο-

CH,

HCH ₂ -CH ₂ -O) ₄ -CO-CH ₂ -CH ₂ -N

«F

Y. CH, -Οι *

CH, -Ο—

-ICH ₂ -CH ₂ -O) ₈ -CO-CH ₂ -CH ₂ -N

CH,

CH,

Z. Be ( —CO- CH ₂ -CH ₂ -N Molver 1 CH ₂ I. \ 3 ge Density of Ver properties drawing ( ratio 1 % Aziridine stick found Product soapy tion : η, —ο— , / - anridinopropionic acid ester Remainder X C: G 1 \ I
CH, substance in the product number : η —ο— from: Mole be 1.99 CH ₂ -O- ge 4: 1 1 calculates 1.12 • \ weight 4: 1 0.9993 ^{: oc} 77.1 yellow viscous liquid B. Poly tetrahydrofuran 1 2.34 0.9958 ^{: or} 48.5 yellowish wax, MG 1000 432 1.27 2.2 Softening point approx. 40 ° C MG 2000 936 3: I. 1 1.03 C. 3: 1 2.6 1.0122 ^{: ot} 98.0 viscous brownish liquid D. I polypropylene oxide 3: 1 1 2.8 0.6 1.0106 ^: " ⁽ 47.9 viscous brownish liquid ι: MG S50 406 2.85 1 1.27 0.58 1.0765 ^: " ^c 98.4 viscous brownish liquid ί MG 2000 986 2.74 3.2 0.83 1.0178 ^{: o (} 28.5 viscous yellow-brown liquid ο; Bisphenol A χ 8 PO 232 2.77 0.74 1.0110 ² " ^c 22.2 brownish viscous liquid H Glycerine χ 84ΡΟ χ 15ΗΟ 1844 0.67 0.83 1.0274 ^{: or} 43.1 brownish viscous liquid 1 Glycerine χ 84PO χ 30KO 2064 3.45 1.1 Glycerin χ 51 PO χ 15l ^: .O 1206 1.45 1.0132 - " ^c ' 40.5 honey-colored dl K Poly tetrahydrofuran 3.09 1.06 MG 2000 χ 10EO 1156 1.02 1.0143 ^{W £} " 57.6 yellow wax type. Subst. Approx. 26 C L. Poly tetrahydrofuran 2.75 1.70 MG 1000 χ 10EO 652 0.97 1,0329 ^{50 (} 42.8 Softening point approx. 40 ° C Poly-t; trahydrofuran 2.77 1.35 0.91 M. MG 1000 χ 20EO 872 2.63 I.O342 ^{: ot} ' 32 cloudy, brownish liquid W. Polypropylene oxide 1.07 4.1 1.0348 ^: " ⁽ " 34 viscous brownish liquid MG 2000 χ 10EO 1206 2: 1 0.91 2.8 X MG 2000 χ 10EO 1426 2: I. 10.0 1.1168 ^2or 187.5 yellow-brown viscous liquid Y Polyethylene oxide 4.7 1.0823 - < ^{| C} UO yellow-brown viscous liquid Z MG 400 176 3.0 1.1511 a> <" 387 pale brown colored viscous MG 750 352 10.9 liquid Glycerin

The derivatives A to M satisfy formula 1. while those used for comparison purposes Derivatives W, X, Y and Z are outside of this formula.

The surface shrinkage and the felting of the goods after 5 machine washes serve as finishing effects assessed with 2 g / l of a commercially available mild detergent in a domestic drum washing machine. The matting is assessed subjectively with grades from 1 to 5, with grade 1 for the strong matting an untreated sample during washing and grade 5 for the surface appearance of the goods before Washing attempt.

Example !

4 (10 g of one of the aziridine derivatives A to E and 11 to M are optionally melted and with HX) g one also melted, the emulsifiable wedge improving polyaddition products of 58 moles of propylene oxide and 1 mole of polyethylene glycol from a molecular weight of 1800 to 2 (K) O to a homogeneous one

Mixture stirred. This is used to mix 50 g of a non-ionic wetting agent consisting of 50 parts

so of the tallow fatty acid ester of an addition product of 40% ethylene oxide on polypropylene glycol with a molecular weight of 2500, 40 parts of the adduct of 40 moles of ethylene oxide in 1 mole of castor oil and 10 parts of water. Pour into this mixture

Stirring by hand for 5s in portions of 500 ml of demineralized Water. After passing through a paste-like state, the emulsion becomes thin. This stock emulsion is stirred into 9 liters of cold water by hand. You get 10 1 equipment fleet,

(«) Which contains 40 g / l of the aziridine derivative. In the same In a way, the aziridine derivative W is used to produce a fleet of equipment.

A double jersey made of wool dyed in the top is impregnated with this liquor, between

6s rollers pressed to 90% liquor pick-up, with stretched to the original width using a needle frame and dried at 130 ° C. for two minutes and reacted with the aziridine derivative.

609 542/473

400 g of one of the water-soluble aziridine derivatives X or Y are dissolved in 9.45 l of demineralized water and 50 g of the nonionopic wetting agent described above are added. 10 l of equipment liquor is obtained which contains 40 g / l of aziridine derivative. The aforementioned knit fabric is impregnated with the Ausrüstungsfk> tte, squeezed between rolls to 90% Fleet View, clamped by a pin frame to output width and 5 minutes |> ei 130 ⁰ C dried and reacted with the aziridine derivative.

To test the finishing liquor that product, together with an unmodified sample lind ballast material in a drum washing machine ■ nit 2 g / l mild detergent at 40 ⁰ C 5 χ 20 minutes rewaschen wherein χ between each wash 5 is flushed with old water. The washed test specimens showed the following results:

product % Shrinkage
Meshes
rows
direction in
Meshes
rod
direction % Areas
shrinkage Vs ; rfilzui Without -19 -10 -27 1 A. - 7th - 4th -11 4th B. - 3 _ 2 - 5th 4th until 5 C. 2 _ 3 - 6 4th until 5 D. - 3 _ 2 - 5th 4th until 5 E. - 8th - 5th -13 3 to 4 H - 7th 5 -12 3 to 4 I. - 3 _ 3 - 6 4th until 5 K - 8th _ 5 -13 3 to 4 L. _ 7 - 6 -13 3 to 4 M. -10.5 - 6 -16 3 W. -17 - 8th -23.5 1 up to 2 X -15 (J -22.5 1 Y -14 -11 -25.5 1

The results show that the products A to E and H to M corresponding to Formula 1 are good Deliver equipment effects. But as soon as the atomic ratio C to O, as is the case with products W, X and Y, drops below 2.67: 1, becomes practical no effect achieved.

Example 2

An off-white single jersey made of pure wool is used to catalyze the subsequent reaction with Impregnated 1% strength aqueous sulfuric acid and dried at 60 ° C. to 10% residual moisture.

The products B and X are each in a concentration of 50 g / l dissolved in perchlorethylene. Samples of the sulfuric acid are impregnated with these solutions vorbchandelte goods, presses them to a liquor pick-up of 100% between rollers and then heats the goods to BO C for 15 minutes.

After testing according to the information in Example 1, the following results are obtained:

product % Curvature in Machine % Area Vcr- Meshes rod- shrinkage felted rows direction direction -24 Without -28 N -45.5 1 B. -15 _25 -19.5 3 to X -25 -43.5 1

While product B corresponding to formula I shows a good effect, product X cannot be used.

Example 3

Two samples of the knitted fabric used in Example 1 are impregnated with an aqueous emulsion containing 50 g / l of product F or G. A third sample of the same product is impregnated with an aqueous solution containing 50 g / l of the product Z and 15 g / l MgCl -, - 6H ₂ O as a catalyst. The three samples are pressed to 90% liquor pick-up and dried for 2 minutes at 130 ° C. and reacted with the ariiidine derivative. After testing according to the information in Example 1, the following results are obtained:

product % Shrinkage in
Mesh-mesh
rows chopsticks
direction direction -10 "/ 0 l-smile-
shrinkage Ver
coincidence Without -19 - 3 -27 1 F. - 4th - 5th - 7th 4 to 5 G - 7th -10 -12 3 to 4 Z -13 -21.5 1 to 2

The data show that Products F and G are well effective as wool finishes while the product Z, which differs from F and G by the lack of polyether chains, is unusable, even though a catalyst has been added to support the reaction.

Example 4

A non-dyed 100% wool single jersey is made with one of the following Impregnated liquors containing products, squeezed to a liquor pick-up of 90%, in a needle so Stretching frame stretched to 90% of the raw material width and dried with 15% lead for 3 minutes at 130 ° C and implemented.

The following products are used:

Aziridine emulsion

40 parts by weight of the product B in the presence of 10 parts by weight of one of the emulsifiability improving polyaddition product of 58 moles of propylene oxide with 1 mole of polyethylene glycol of molecular weight 1800 to 2000 and 5 parts by weight of the wetting agent described below through the portions Addition of 50 parts of water at room temperature by stirring cmulgicrt.

Polyacrylate 1

50% aqueous dispersion of a copolymer * made of 43% n-biitylacrylate. 3% acrylonitrile. 3% N-methylolacrvlamide and 1% acrylic acid.

Polyacrylate II

40% aqueous dispersion of a copolymer of 90% n-butyl acrylate, 7% acrylonitrile, 2.5% 3-chloro-2-hydroxypropyl acrylate and 0.5% acrylamide.

Polyacrylate 111

40% aqueous dispersion of a copolymer of 89% n-butyl acrylate, 5% 1,4-butanediol diacrylate, 3% acrylamide and 3% N-methylol acrylamide.

Aminoplast I.

80% aqueous paste of a Ν, Ν'-dimethylolurea etherified with methanol.

Aminoplast II

50% aqueous solution of N.N'-dimethylolethyleurea.

Wetting agents

Mixture of 50 parts by weight of an ester of tallow fatty acid and an addition product of 40% Ethylene oxide with a polypropylene glycol with a molecular weight of 2500, 40 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil and 10 parts of water.

sample
a

100

100

100 50 100

50

100

100
50

Aziridine emulsion, g / 1
Polyacrylate 1, g / l
Polyacrylate II, g / l
Polyacrylate III, g / l
Aminoplast I, g / l
Aminoplast II, g / l
Ammonium chloride, g / 1
% Shrinkage (area)
Matting note

For sample b, the single jersey made of 100% wool was treated with 2% of an investment product of 40 moles of ethylene oxide before finishing on 1 mole of castor oil, 5% ammonium sulfate in water, pH 6.0. Liquor ratio 1:30, heated to 98 ° C for 90 minutes (so-called blind Coloring).

45
1

16

10 50 20th 10 10 5 5 18th 5 21 5 4th 14th 3-4 21.5 4-5 3-4

The wool material used here is so inert, that it does not yet react with product B under the chosen conditions (see sample a in Comparison to the blank sample g). But if you treat it beforehand in the usual way for dyeing, you get the equipment is faultless without changing the other conditions (see sample b). Similar results is achieved by using an aminoplast, an acetalization catalyst and a dispersion of a film-forming acrylic ester polymer (see samples c to 0

Example 5

An off-white single jersey made of 100% wool with a ^{weight per unit area of 215 g / m 2} is impregnated according to the recipes given in the table below with an aqueous solution of pH 4.5 which contains activator I, II or III in addition to a wetting agent. The liquor uptake is about 80%. The goods are dried for 3 minutes at 130 C.

After this activating pretreatment with reducing agents, the goods are padded with 100 g / l of the aziridine emulsion and pressed to a liquor pick-up of 80 to 90%. The goods are wrapped on a roll, left to roll for an hour and dried in a hot air drum dryer at an air temperature of 70 C. The samples are provided with shrink marks and in a drum washing machine 5 washes at 4 ° C. with 2 g / 1 subjected to a mild detergent. They are then left to dry without tension, the surface shrinkage that has occurred is released and the interlacing is assessed as indicated above.
Ini.u'iide products are used:

Activator I.

70% solution of ammonium hydrogen sulfite [(NH ₄ ) HSO,]. which "was adjusted to a pH of 4.5.

Activator II

50% solution of sodium disulphite (Na ₂ S ₂ O ₅ ) with a pH of 4.5.

Activator 111

70% solution of triethanolammonium hydrogen sulfide (OH - CH ₂ -CH ₂ I ₁ NH HSO, with a pH value of 4.5.

The wetting agent

Mixture of 50 parts of the tallow fatty acid derivative of an addition product of 40% ethylene oxide Polypropylene glycol with a molecular weight of 2500. 40 parts of the adduct of 40 moles of ethylene oxide of 1 mole of castor oil and H) parts of water.

Aziridine emulsion

40 parts by weight of product B are marked with H) parts by weight of the investment principle of 40 moles of propylene oxide and 1 mole of polyethylene glycol of molecular weight 2 (K) O mixed and 50 parts of water at 20 to 25 ° C. were added in portions with stirring. the Emulsion contains 40 percent by weight of the aziridine equivalent.

template 50 5 b 5 C. template a 4.5 ._ 4.5 a b c Activator I (g / l) - SO 135 80 - pH value 6.5--7 6.5-7 6.5-7 Activator II (n Il _ 120 Fleet 80 80 80 Activator 111 (g'l) 3 minutes at 130 C 5 recording (%) Center of the net! (g / l) 100 100 4.5 Stay wet rolling for 1 hour at room temperature PH value SO IO
The equipment musicians a to c and an untreated Fleets tes pattern d are sewn together and incorporated recording (%) on a reel skid, coming in wet, in the fleet Drying in hot air 100 ratio 1:30 (based on the dry weight of the Aziridine emulsion _1S goods) 90 minutes at 98 C colored with

1.5% of the 1: 2 chromium complex Ci, of 4-chloro-2-aminophenol-6-sulfonic acid)

--► l-Phenyi-3-mc! Hy) pyrazolone- (5) J 5% (NH ₄ I ₂ SO ₄

pH 6.0

based on dry weight
the goods

This is followed by rinsing with cold water, centrifuging and for 50 minutes at 70 C in a drum dryer Warm air dried. The equipment musicians a. b and c are colored red in the same tone and show a clear color Mesh structure, while the pattern d is colored in a lighter iRed than the patterns a to <_ and a blurred one Mesh structure with clearly recognizable matting. The patterns come with a Provided area markings and subjected to the washing test.

5 delicate washes at 40 C with 3 g / l sodium dodecylbenzenesulfonate

template

Area shrinkage (%) 6 7.5 6.5
Matting 4.5 4.5 4.5

Example 6

An off-white gabardine made of 100% wool with a weight per unit area of 210 g / m ² was padded with 50 g of 1 of the activator and 5 g of 1 wetting agent (both according to Example 5) at a pH of 4.5. pressed to a liquor pick-up of 50% and treated with saturated steam for 5 minutes on a wet decanter and then filtered off with suction for 5 minutes. The goods then had a residual moisture content of 21%.

The pre-activated tissue was divided into three equally sized samples.

Sample a was on the reel vat with 5 g 1 of the aziridine emulsion according to Example 5 in water The liquor ratio 1:50 is allowed to run for one hour at room temperature and at pH 6.5 to 7. then drained the liquor, rinsed it once with cold water and colored it (see below).

Sample b was padded with 80 g / l of the aziridine emulsion. pressed to 70% liquor pick-up. Left to roll for one hour at room temperature as a stick and colored (see below).

Pattern was colored without further treatment.

For the coloring, the 3 patterns were sewn together and on the reel skid in the liquor ratio Dyed with 1:30 (based on the dry weight of the goods) 90 minutes at 98 ° C

1.5% of the dye mentioned in Example 5

5% (NHJ ₂ SO ₄
pH 6.0

based on the dry weight of the goods

It was then rinsed with cold water and placed on a pin tenter frame with the fabric guiding with little tension Dried at 110 ° C. for 2 minutes.

The samples a and b were colored in a deeper RoI than the Musler c. They showed a smooth surface. while pattern c is heavily lined with running folds was streaked.

The three samples were provided with markings and subjected to the washing test.

The following shrinkage was obtained:

template b C. Λ -5.5 .... 24 "η areas -6.5 shrinkage nlatt. stronger Surface image ulati. no Moiiv no Ver Effckt. Vcr- lilzunii distinct lilzuni! Vcrfil / iniL

Samples a to c were tested prior to washing the Naßkniltcrwinkcl after Too ta 1 (see British Patent 7 27 890) measured. The following results were obtained;

Miisk-i

Wet knee angle 107 113 78 chain 148 168 119 Shot

As shown in pattern a, the fabric pretreated with activator 1 also takes on product B. Peeling process on.

Samples a and b are not only characterized by slight matting and shrinkage in the washing test, but also distinguished by a significant increase in the wet crease angle.

Example 7

An off-white poppel jersey made from HKl ¹ O wool. Elacheiiieweight 340 g no. was pretreated with activator 1 like sample a in example 5 and dried in hot air at 130 ° C. for 3 minutes. The activated goods were then treated with a solution which contained 60 g of I of the aziridine derivative B in perchlorethylene. The goods were pressed to a liquor pick-up of 90% and the solvent was evaporated by laying out in the air. The finished knitted fabric was then provided with markings and subjected to the washing test described above. The following values of the shrinkage and the volume were obtained.

encapsulation s ρ i C W .11 "κ area cr 24 Matting at 1 1 8

W arc ii ..
example

S. 4th

A top dyed simple .lerses made of 100% wool with a ^{surface weight of 225 g / m 2} is impregnated with an aqueous liquor which is composed according to the recipe given below (the designations of the components are the same as in Example 5) (see sample a). a second sample of the same material with a liquor that contains only wetting agents (see sample b). It is pressed to a liquor pick-up of 80% and the samples are left to roll in foil for 24 hours at room temperature. Then it is left to dry by laying on air, wrinkle marks are applied and washed five times in a drum washing machine at 40 ° C. with 3 g of sodium dodccylbenzene sulfonal; Laundry detergent. After drying in air, the surface shrinkage is read off and the filing is assessed.

The following results were obtained:

Activator 1 (g Il
Wetting agent (g 1)
Aziridine emulsion (g 1)
pH of the emulsion
Surface reduction (%!
Verfilzuni!

l'robc

30th

'S

90

5.5
6.5
4.5

* 09 542Λ

Claims (3)

Patent claims: 1. Compound of the general formula I containing aziridine radicals Q X-C-C-C-N in which R ₁ to R _{7 are} hydrogen atoms or low molecular weight alkyl radicals, Q is the radical of an alcohol or phenol with a molecular weight of 62 to 300, η 2 or 3, X is a polyether chain of butoxy and / or propoxy and optionally ethoxy units with a Atomic ratio C: O of at least 2.67: 1 and a molecular weight of 150 to 1500 when ti = 2 and from 150 to 3000 when / i - 3. 2. Compounds containing aziridine residues according to Claim ! with / 1 = 2, characterized in that the part of the molecule —X-Q — X— from the divalent residue of a polytetrahydrofuran chain with a molecular weight of 1500 to 2500 consists. 3. Use of a compound according to claim 1 or 2 as an active ingredient component in one Equipment bath containing protein fibers to reduce shrinkage and matting or goods consisting of it.