DE2334655A1 - COMPOUNDS CONTAINING AZIRIDINE RESIDUES AND THEIR USE TO REDUCE THE RUNNING AND FELTING OF PROTEIN FIBERS, OR GOODS - Google Patents

Description

Our reference: O. Z. 29 993 Rt / Wll 67OO Ludwigshafen, July 6, 1973

Compound containing aziridine residues and its use for reduction the running-in and felting of protein fiber-containing or consisting of material

The present invention relates to new aziridine radicals containing Compounds and an improved method for reducing shrinkage and tangling of protein fibers containing or resulting goods by implementing them with these new connections.

For example, by St. B. Sello and G. C. Tesoro, Applied Polymer Symposium No. 18, 629 (1971) are reaction products of polyalkylene oxides with diisocyanates and ethyleneimine as a wool finish is well known. However, they are difficult to emulsify and have a strong tendency to have a very high on the foulard rollers to form annoying sticky coating.

It is known from German Patent 1,265,114 to reduce the shrinkage and felting of fibers, threads, yarns and fabrics made of wool and silk by treating the materials with solutions containing 1 to 10 % of a water-soluble aziridine compound of the general formula

CH - N,

LR ₄

contain, soaked, then dried and reacted with the aziridine compound, where in the general formula η 2 or 3, R ₁ * R ₂ and R-, hydrogen atoms or lower alkyl radicals, R ^ hydrogen, a lower alkyl radical or an OH group and A denotes an n-valent radical from the group of alkylenes, aralkylenes, oxalkylenes, hydroxyl-substituted alkylenes, SOp-containing alkylenes, a carboxylic acid ester radical and a radical having conjugated double bonds, bonded to the rest of the molecule through CC bonds.

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In the French patent 1 5 ^ 4 210 are under one A larger number of esters from polyols and aziridine carboxylic acids summarized also disclosed those whose polyol component of Polypropylene glycols with molecular weights up to 20,000 are derived; the entire class of substances will, among other things, also - however in very general form - recommended for changing the properties of wool.

After knowing this doctrine, which was announced in the above-mentioned writings, one had to assume that keratin fibers were basically involved any compounds that contain 2 or 3 aziridine rings as functional groups and can be made felt-free through which a crosslinking of the peptide chains of the keratin fibers takes place. An influence of the type and molecular weight of group A. The above formula on the effectiveness of the product was not to be expected according to the state of the art.

It must therefore be surprising as among the bisfunctional atninoaziridines Some special products with very specific molecular weight ranges have been found that show themselves in a conspicuous manner with regard to their effectiveness for the anti-felting finishing of keratin fibers. These powerful products are in the mentioned writings are not mentioned. These new substances correspond to the general formula

0 R-, R, s ^ R ₆

Ii r 3 ι 1 /

QfX-C-C-C-N

R. R \

I,

in which R »to R _{7 are} hydrogen atoms or low molecular weight alkyl radicals, Q is the radical of an n-valent alcohol or phenol, η 2 or 3 * X is a polyether chain composed of butoxy and / or propoxy and optionally ethoxy units with an atomic ratio of C: 0 of at least 2.67: 1 and a molecular weight of 150 to 15ΟΟ at η = 2 and from 150 to 3000 at η = 3.

Low molecular weight alkyl radicals are, for example, those having 1 to 3 carbon atoms, such as, in particular, methyl; however, those substances of the formula I which have hydrogen atoms as radicals R to Ry are preferred.

409886 / U23

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It has also been found that a method for reducing the shrinkage and entanglement of protein fibers can be used containing or consisting of material by impregnation with a finishing bath that has at least one connection with contains several aziridine residues, and reaction of the aziridine residues with the protein avoid the disadvantages mentioned and improve them than the previous results can be achieved if you have at least one substance as a compound containing asiridine residues Formula I used.

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

Q (H) _n II

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

H) _n III

added - or by adding a polyether of the formula III by polymerization of tetrahydrofuran and / or one or more Produces alkylene oxides, so that the entire molecular group -X-Q-X-optionally consists of a single polyether - and with this polyether a ß-aziridinocarboxylic acid ester of the formula "

"'3 ti y / I ^R 6

RO-CCCN _π ° IV

R ₄ R ₂

η-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- to B- in formula Γ7 have the meaning given above for formula I.

Preferred n-valent alcohols or phenols are those with a molecular weight of up to 300. It can be allphatic, cycloaliphatic or aromatic poly-

409886 / U23 _{/ 4}

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alcohols to mononuclear or polynuclear polyphenols or also to Trade substances with phenolic and alcoholic hydroxyl groups. Examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycols, hexanediols, diethylene glycol, Dipropylene glycols, dihydroxydibutyl ether, glycerine, hydroquinone, resorcinol, catechol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, pyrogallol, phloroglucinol, Saligenin.

The type and amount of the components to be added or polymerized onto the substances of the formula II, like the addition or polymerization conditions, are selected in a manner known per se so 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 accordingly consist of pure butoxy or propoxy units, they can also contain both butoxy and propoxy units; In addition to these units mentioned, they can also contain so many ethoxy units that the atomic ratio does not fall below the mentioned atomic ratio. Polyether chains which are built up only from ethoxy units have an atomic ratio of C: 0 such 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 is of the polyether group X- in the range from 150 to 1500, preferably 200 to 125Oj, with η = 3, it is 150 to 3000, preferably 200 to 2200.

At η = 2 they then have a pronounced optimum effect, when the molecular weight of the group -X-Q-X- is about 2000. The effectiveness increases in the event of deviations from this on both sides continuously from. For substances with η = 3 the optimum is not so clearly pronounced.

It is not of essential importance for the effectiveness of the substances of the formula I how different alkoxy units are are distributed in the chains X. Accordingly, the alkoxy units can be linked to one another, for example

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O- ζ. 29 993

Blocks are present (cf. the schematic formulas V bix X); but they can also be distributed statistically over the chains (cf. the schematic formulas XI to XIV); finally are Mixed forms of these two extremes are also possible (cf. the schematic formula XV):

VI

VII

VIII

IX

a- (BO

a. (BO]]

b. (EOj] "

(PO) T _ b. (EO)

BO = butoxy-, PO = propoxy-, EO significant.

XI XII XIII

XIV

XV = ethoxy radicals,, each two--

The indices a, b and c used in formulas V to XV represent positive numbers selected so that the Molecular weight and carbon-to-oxygen ratio conditions listed above be respected.

The substances of the formula III obtained by polyaddition or polymerization are known to be non-uniform substances, but mixtures of substances of different chain lengths, which are referred to in English as "cogeneric mixtures" xrground. Therefore the information is about molecular weights

409886 / U23 _{/ 6}

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and to understand atomic ratios as mean values.

β-Aziridinocarboxylic acid esters of the formula IV are known or so far they have not yet been described - accessible by processes known per se, for example by reacting acrylic, Methacrylic or crotonic acid esters or of ß-chlorocarboxylic acid esters with aziridines.

The substances represented by the general formula I are not or not completely soluble in water at room temperature. They can be mixed in water, preferably with non-ionic or cationic .M.iuljaLoren in feiiidisperse, very persistent Transfer emulsions or dispersions.

Depending on the type of cheese w_ iie substances of formula I are included Fluid or solid at room temperature. Especially with fixed Products has been preserved by mixing them with anhydrous Auxiliaries, such as emulsifiers, wetting agents, anti-migration agents or calibrators, in one at room temperature bring liquid consistency. Through the appropriate selection of these tools it can be achieved that the production of the Emulsions are made by pouring water into the liquid product mixture without the additional use of emulsifiers can.

To prepare the equipment fleet, a stock emulsion can first be used be prepared by adding the same amount of cold v / ater to the product with mechanical stirring. Depending on Type of emulsifiers or auxiliaries used, this emulsion can initially take on a paste-like consistency, but that after adding more water it becomes thin and pourable. This stock emulsion is used without slow agitation of the equipment liquor added. If necessary, it becomes a nonionic one or a cationic wetting agent is added and the pH of the bath is adjusted.

The stability of the aqueous dispersions or emulsions of the Substances of the formula T depend, among other things, on the pH value. If their pH is below 4, the aziridine rings - depending on the

409886 / U23 _{/ 7}

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Degree of dispersion - usually split so quickly that the effectiveness of the products quickly deteriorates. However, in the pH range from 5 to 10, preferably from 5 to 7, the stability of the aqueous preparations containing 2.5 to 5% product is generally at least 12 hours, which is sufficient for practical purposes.

The limited shelf life of the substances of the formula I in the presence of water means that these products are in the anhydrous Condition must be stored in order to ensure their effectiveness for a period of at least 6 months.

The emulsions or dispersions of substances of the formula I can be applied without difficulty by customary methods to goods containing or consisting of protein fibers, eg. B. on fibers, threads, tops, yarns and woven and knitted goods made of wool or silk. The permanent fixation of the products on the polypeptide-containing substrate can take place after drying, preferably at temperatures of up to 150 ^° C. and pH values of 5 to 10. If the protein fibers are sufficiently reactive, no catalysts are required to carry out the fixation reaction.

The reactivity of protein fibers depends, among other things, on their pretreatment. It has z. B. found that a pretreatment of the goods to be equipped with aqueous liquor at elevated temperature increases the reactivity of the protein fibers so that that there is no need for catalysts. Such a pre-treatment 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 reaction with the aziridine residues can occur supported by catalysts. Metal salts, for example, such as those used as acetalization catalysts, are suitable as such in the reaction of cellulose with N-methylol groups are common; Zinc nitrate, magnesium chloride and especially zinc sulfate may be mentioned. It is convenient to use these catalysts before impregnating the goods with the equipment

409886 / U23 / 8

- 8 - 0.3.29 993

to apply fleet on this. Free acids, e.g. B. sulfuric acid, act catalytically in the desired sense, if they are applied to the goods to be equipped beforehand; however, they have the disadvantage that they reduce the pH of the equipment liquor, which is located in the impregnation device, lower and thus can affect their durability.

Another way to aid the reaction between the protein fibers and the aziridine residues is to the finishing bath apart from at least one substance of the formula I and optionally the other auxiliaries mentioned above 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 a dispersion add at least one film-forming acrylic ester polymer.

Low molecular weight N-methylol and / or N-methylol ether groups containing substances are z. B. as a finishing agent for cellulose fibers is generally known and used. It is preferably to substances with a molecular weight up to 350 * the contain two or more groups of the formula -CHp-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 with preferably 1 to 4 carbon atoms. as particularly preferred substances of this type are those of the general formulas

It

R _n O-CH ₀ -N N-CH ₀ -OR ₁ XVI

or 0

R _1n O-CH ₀ -NX) -A-fo-CN-CH ^ ₇ -H XVII R ₁₂ 0 R ₁₃ OR _n

highlighted, where R _{1 and R 0 are} hydrogen atoms or low molecular weight alkyl groups, R ₃ and Rj ₊ radicals of the formula

409886 / U23 ^{/ 9}

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22 ■] :, 655

R, -

-c t

^R 6 the immediately or above

h h

-C-, -0- or -N-t

are connected to one another, or hydrogen atoms, low molecular weight alkyl groups or low molecular weight alkoxymethyl groups, R, RR and R ,, hydrogen atoms or low molecular weight alkyl groups, Rs and Ko '.' / assc ^ scoiraGome, hydroxyl groups, low molecular weight alkyl groups or low molecular weight alkoxyl groups, a lower ₁ col ^ jax : Ue Aiicyi ^ mppe or an aiederui ^ le

Hydroxyalic.yl group, R, _o and R ₁ ■ * water eof f atoms, low molecular weight alkyl groups or low molecular weight alkoxymethyl groups, A is a divalent aliphatic hydrocarbon radical with 2 to 8 carbon atoms and Z is zero or 1. The radicals R-, to Rg and R ^ ₀ to R, ^ defined together can be identical or different. Preferred low molecular weight alkyl, hydroxyalkyl, alkoxyl and alkoxymethyl groups are those which contain 1 to K carbon atoms in the alkyl moiety.

Examples of substances of the formula XVI include: derivatives of urea, monoalkyl and symmetrical JJialkylharastoffen which contain at least 2 hydroxymethyl groups or low molecular weight alkoxymethyl groups, such as Ν, Ν ¹ -dihydroxymethylurea, N, N'-dimethoxymethylurea, N, N'-dibutoxymethyl -N-methylurea, N, N ', N ^! -Trimethoxymethyl-N-ethylurea and N, N ^! -Diethoxymethyl-N, N'-dimethylurea, the Ν, Ν'-dihydroxymethyl derivatives and low molecular weight N, N'-dialkoxymethyl derivatives of H, N ^f -ethylene urea '(= imidazolidone-2), N, N ¹ -1,2-propylene urea (= 4-methylimidazolidone-2), N, N ^l -l, 3-prop7 / lenurea (- N, I <i "-trimethylene urea or hexahydropyrimidone-2), 5-hydroxyhexanydropyrimidone-2, 4-hydroxy and 4- Alkoxy-55 5-dialkylhexahydropyrimidone with low molecular weight alkyl and alkoxyl groups, hexahydro-1,3,5-triazinon-2 and its 5-alkyl- and 5-hydroxyalkyl derivatives, glyoxalmonourein (-4,5-dihydroxyimidazolidone-2) and urons.

409886 / U23

ORIGINAL INSPECTED

ίο - c.z. 29 993

Examples of substances of the formula XVII are the hydroxymethyl derivatives and the low molecular weight alkoxymethyl derivatives of Mono- and dicarbamic acid esters (= mono- and diurethanes), such as Carbamic acid ethyl ester (urethane in the narrower sense), carbamic acid propyl, -butyl- and -octylester, N-methylcarbamic acid ethyl ester, N-ethylcarbamic acid butyl ester, dicarbamic acid ester and di-N-ethyloarbamic acid ester of ethylene glycol, 1,3- » 1,4-butanediol and 1,6-hexanediol.

In addition, however, other low molecular weight N-methylol and / or N-methylol ether groups are also used for the present process containing substances into consideration, for example optionally etherified N-methylol compounds of aminotriazines, such as Melamine, ammeline and ammelide, from guanidine, dicyandiamide and dicyandiamidine, Thiourea and acetylenediurea (= glyoxaldiurein).

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

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

Acetalization catalysts are used in the finishing of fiber material generally used with equipment. They are usually somewhat imprecisely referred to as curing catalysts. It are preferably latently acidic salts, d. H. Salts that are not or only slightly acidic by themselves, but through Hydrolysis, thermal influence or the like release so much acid that the reaction between the fiber material and the equipment is accelerated. Latent acid salts are mainly salts from ammonia, amines or polyvalent salts Metals and medium-strength or preferably strong acids, for example ammonium chloride, ammonium sulfate, ammonium phosphates, Ammonium nitrate, di-monoethanolammonium hydrogen phosphate, Ethanolammonium chloride, l-Hydroxy-2-methylpropylarnonium - 2-

A09886 / U23 / n

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Chloride, magnesium chloride, aluminum chloride, zinc chloride, zinc nitrate, Zinc sulfate and zirconyl chloride. The catalyst is chosen in the usual way according to the intended working conditions the end. In some cases it is advantageous not to use individual substances but rather mixtures of several substances as catalysts to use. Also strong or medium strong inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, Glycolic acid, maleic acid, monochloroacetic acid, triehloroacetic acid, Tartaric acid and citric acid have a catalytic effect in the desired sense, but the following apply to their applicability same limitations as above for their use to catalyze the reaction between protein fibers and aziridine residues specified.

Dispersions of film-forming acrylics; polymers are available as Aids in the finishing of textile fiber goods in general known and widespread. For the purposes of the present invention, especially those polymers come into consideration that besides those responsible for the film-forming properties Acrylic ester units and, if appropriate, units of other olefinically unsaturated monomers, crosslinkable groups, are incorporated in the form of polymerized units contain, for example, unetherified or etherified N-methylolacryl and methacrylamide groups and epoxy or Halohydrin groups. Such dispersions of film-forming acrylic ester polymers are z. B. in the German interpretative writings 1 047 431, 1 110 6O6, 1 209 9Ö9 * 1 494 87I, der German Patent 1,140,898 and U.S. Patents 2,719,072, 2,780,608, 3,078,185 and 3,100,674.

The concentration of the treatment bath in the components discussed depends on the impregnation devices used and the desired liquor uptake in a manner known per se. It is chosen so that the following amounts of the constituents are applied to the goods to be finished: 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).

409886/1423 ^{/ 12}

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

The merging of drying and fixing has in particular proven in the finishing of knitted fabrics To avoid tension deformation of the goods, which are sensitive to warpage, before fixing.

If the goods padded with the finishing liquor are dried in the temperature range from 60 to 80 ° C, the reaction takes place Aziridines with the polypeptides of the goods to be equipped have not yet taken place. A product 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 resistant to felting and shrinking mechanical washing machines and in drum dryers (e.g. Tumbler) protected. The temperature of the ash liquor should preferably be 40 ° C .; it can with slightly lower requirements the dimensional stability can be increased up to 60 ° C.

When materials are made from protein fibers that have been pre-dyed with acid or reactive dyes, the substances of the formula I do not impair the general fastness properties of the dyeing, or only in exceptional cases only slightly. The same applies to the fastness of dyeings on some of the man-made fibers based on polyethylene terephthalate, nylon 6,6, nylon 6 and polyacrylonitrile.

A09886 / U23

- ι? - O.Z. 29 993

Dyeings with direct and reactive dyes on cellulose fibers can be lightfast with substances of the formula I are impaired, but protein fibers are comparatively little mixed with cellulose fibers.

Materials made of protein fibers can also after finishing with the substances of the formula I in the usual way with acid and Reactive dyes are colored. The winding speed the coloring is in many cases increased by the finishing products. This way of working has the advantage that the Dyeing of already finished goods on reel runners or other particularly economical dyeing machines ev-fol "". ^ l- ^ nr., without the risk of matting ^ ^ he goods consists.

In a particularly preferred embodiment of the invention Procedure, which is particularly important in the case of kera ^ iribaltigem Fiber good has proven itself, one proceeds in such a way that one sur relief the · implementation of the / ^ iridine residues with the pr o to in the to be equipped Well before or during the impregnation with i ^ m treatment bath treated in a known manner with a solution that contains an inorganic or organic salt of sulphurous acid, and the material treated in this way with the salts of sulphurous acid Lets acid react.

Examples of suitable salts of sulphurous acid are: Sodium sulfite, sodium hydrogen sulfite, sodium disulfite, ammonium hydrogen sulfite, triethanolammonium hydrogen sulfite.

So you can use this process variant -swsibadig or single-bath carry out -

In the two bath process procedure by first impregnating the fabric with an aqueous solution of a sulphite salt, vorzusweise in the pH range of 4 to 5 × It has proven useful to measure the amount of sulphite sais so zn that 1 to 3 / <> SO ₂ * based on the dry weight of the goods on which st, .. lit. The goods treated in this way are then either stored on rollers for 24 to 48 hours wet at normal temperature

409886 / U23

BATH ORIGINAL

- 14 - Ο.Ί. 29 993

or dried and heated or heated in a wet state. The heating can be carried out in the usual way with contact heat, radiant heat, hot air or steam, depending on the moisture content of the goods. It has proven useful to bring the temperature of the goods to at least 100 ^° C .; they are preferably heated to between 100 and 150 ° C. Heating times of 2 to 5 minutes are sufficient for this. The material treated in this way can then be impregnated, as explained above, with the finishing bath which contains the substance of the formula I, and treated further, as also explained above. Keratin-containing pasers are activated by the pretreatment with sulphurous acid salt in such a way that they react with the substances of the formula T even at normal temperature; goods of this type that have been impregnated with a finishing bath therefore only need to be superimposed on themselves at normal temperature for 30 to 120 minutes in order for the reaction to take place. This is done expediently by winding up the impregnated and squeezed-off goods and keeping the winding horizontally in a rotating motion the entire time. The substances of the formula I can also be allowed to act from a long liquor on the material pretreated with sulphurous acid salts by agitating it in an aqueous bath containing substances of the formula I for 45 to βθ minutes. Another possible variant consists in drying the material pretreated with sulphurous acid salts and impregnated with the finishing bath at any temperature, because the reaction between the protein and the substances of the formula I is not linked to the presence of water. Finally, there is also the possibility of applying the substances of the formula I from organic solvents, for example from chlorinated hydrocarbons; these then only need to be evaporated and the equipment is ready.

In the single-bath method, the treatment of the equipment to be carried out is carried out Good things with sulphurous acid salt and with substances of the formula I at the same time. As sulphurous acid salts like all Electrolysis affects the stability of emulsions in general, that is, of emulsions of the substances of the formula I as well care should be taken when combining the two components. In particular, it should be ensured that the

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Equipment bath no more than 15 g / l SOp as sulphurous acid Salt and no more than 50 g / l substance of formula I. In addition, it has proven useful to use the aqueous solution of the sulphurous acid salt as extensively for the preparation of the finishing bath pre-dilute as possible and stir the above-mentioned stock emulsion of the substance of the formula I into this. Farther In the interest of sufficient resistance 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 one-bath process, in which sulfite and aziridine compounds are common in the equipment fleet to use those compounds of the formula I whose group X has a molecular weight of at least 600, preferably over 700 if η = 2, and at least 400, preferably over 500 »if η = 3, and where (regardless of the size of n) that C: 0 atomic ratio of X is at least j5.

The item to be equipped is impregnated with the bath prepared in this way and then, as above, for the first stage of the two-bath working method explained stored at ordinary temperature or heated dry or wet. It has also proven to be particularly effective to dry the impregnated goods first at temperatures around 100 ° C and then for about 5 minutes at about 100 ° C with steam to treat.

The use of sulfuric acid salts in one or two baths in the process according to the invention enables a particularly gentle treatment of the fibers Carried out because only moderate temperatures are required at which protein fibers are not damaged.

The aziridine derivatives A to M and W to Z used in the examples were obtained by transesterifying the diols or triols with methyl β-aziridinopropionate won. They correspond to the following formulas:

A: 0

CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-

■ (CH ₂ - CH ₂ - CH ₂ - CH ₂ - O) ₆ - CO - CH ₂ - CH ₃ --N

.CH, ^ CH,

4 09886 / U23 ^{/ l6}

u.z. 29

CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-

B: 0
t

CHp- CHp- CH ₀ - CH ₀ -O-

H ^ -C-CH-OC: ³ '

CO-CH ₂ -CH ₂ -N

/ CH ₂ ^ CH ₀ .

^IH 2

H ^ C-CH-O-CH ₂ -O

0-

CH

E: H, CC-CH 3

i- / ^C

UC ₀ H, (CH,) - 0 -). CO-CH ₀ -CH ₀ -N ^ |

CH ₂ J

0-

CH ₂ -O-

P: CH -0-

CH ₂ -O-

CH,

- (C ₂ H ₅ (CH ₅ ) -0 ^ fCH ₂ -CH ₂ -O) ₅ -COCH ₂ -CH ₂ -N ^ I

CH,

CH ₂ -O-CH -0-CH ₂ -O-

(CH ₅ ) -O) ₂ -Q- ^ CH ₂ -CH ₂ O) ₁₀ -CO-CH ₂ -CH ₂ -N <^ I

^{! H} 2j

-0-

H: CH -0-CH ₂ -O-

J: p (

1- (CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) ₁₃ f CH ₂ -CH ₂ -O) ^ COCH ₂ -CH ₂ -N

(CH ₂ ) ₄ -0-

K: 0
t

- (CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) ₆ - (CH ₀ -CH ₀ -O) ₅ -COCH ₀ -CH ₀ -N ^ I

L: O

(CH ₂ ) ^ - O-

j-CH ₂ -CH ₂ -CH ₂ -O ^ CH ₂ -CH ₂ -O ^ -QCO-CH ₂ -CH ₂ -N-.

4 0988 6 / U23

CH ₂ - ^CH 2

/ 17

O.Z. 29

M: H-, C-CH-O- JS t

CH ₂ -O-CH,

- (C ₂ H ^ (CH ^) - O) -P ^ -CH ₂ - CH ₂ - _{O) 5} - CO- CHg- CHg-N

• 7: H.C-CH-0-

CH _p -0-CH ₀ -O-

CH “-0- tc!

CII ₀ -O-

- (CH ₂ - CH ₀ -O) ^ -CO-CH ₀ -CH ₀ -O), _η - CO-CH ₀ - CH-N |

4 CH ₂ - 0Ή _? - 0) ₈ - CO- CH, -CH,

-CH,

CH, I ^c

CH,

.CH,

CF -0-

CH-O-CH ₀ -O

"Γ

-CfL

409886/1423

Table e

CD
CO
00

description

S-aziridinopropionic acid ester
from:

Remainder X

Molecular weight content

A poly-tetrahydrofuran MW 1000 432 4: 1

E "MG 2000 936 4: 1

C polypropylene oxide MW 85O 40o 3: 1

j "MG 2000 986 3: 1

7, bisphenol A χ t PO 232 3: 1

F glycerine 84 PO χ 15 EO 1844 2.85: 1

G "χ 84 PO χ 30 EO 2064 2.74: 1

H "χ 51 PC χ 15 EO 120C 2.77: 1

"Poly-tetrahydrofuran MW 2000 115c 3.45: 1

10 EO

K "MG 1000 χ D52 3.09: 1

10 EO

L "MG 1000 χ 872 2.75: 1

20 EO

M polypropylene oxide MW 2000 χ 10 EO 12Oc 2.77: 1

W "MG 2000 χ 10 EO 1426 2.63: 1

X polyethylene oxide MW 400 176 2: 1

Y "MW 750 352 2: 1 Z glycerine

% Aziride synthetic
in the product
calculated found 1.99 2.34 1.12 1.27 2.2 2.8 1.03 1.27 2.6 3.2 0, c 0.74 0.56 0.67 0.83 1.1 0.83 1.0c

Density of the product

Saponification number

properties

1.35

1.07
0.91
4.7
3.0
10.9

1.45
1.02

0.97
C, 91
4.1
2.6
10.0

0.9993
0.9958

2C ° C 20 °

, 20

20 °

1.0122
1.0106
I, 07o5 ² ° ₀ 1.0176 ^2C _o

1.0274 ² 1.0.43 *> °

1.0329

1.0342
1.0348

20 °

20 ° 20 °

1,110 &
1.0623 ²⁰

1.1511

20 ¹ -

77.1 48.5

9b, 0 47.9 9c, 4 2 &, 5 22.2 43.1 4C, 5

57, c 42.6

187.5 110 387

yellow viscous liquid

yellowish wax, softening point c ». 40 ° C

viscous brownish liquid

yellow-brown "brownish viscous liquid

honeyed Cl

yellow wax type. 3 years approx 2c ^c

Softening point approx.

cloudy, brownish liquid viscous brownish liquid yellow-brown viscous liquid

pale brown colored viscous liquid

NJ W CjO

- 19 - O.Σ. 29

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

Surface shrinkage and matting are used as finishing effects of the goods after 5 machine washes with 2 g / l of a commercially available mild detergent in a domestic drum washing machine judged. The matting is assessed subjectively with grades from 1 to 5, with grade 1 indicating the strong matting of an untreated one Sample during washing and grade 5 corresponds to the surface appearance of the goods before the washing test.

example 1

400 g of one of the aziridine derivatives A to E and H to M are optionally melted and mixed with 100 g of a likewise melted, emulsifiability-improving polyaddition product of 58 moles of propylene oxide and 1 mole of polyethylene glycol with a molecular weight of 1800 to 2000 to form a homogeneous mixture. This is used to mix 50 g of a nonionic wetting agent, consisting of 50 parts of the tallow fatty acid ester of an addition product of 40 % ethylene oxide with polypropylene glycol with a molecular weight of 2500, 40 parts of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil and 10 parts of water. 500 ml of demineralized water are poured into this mixture in portions while stirring by hand. After passing through a paste-like state, the emulsion becomes thin. This stock emulsion is stirred into 9 liters of cold water by hand. 10 equipment liquor is obtained which contains 40 g / l of the aziridine derivative. The aziridine derivative W is used to prepare a fleet of equipment in the same way.

A double-knit-knit fabric of dyed in the sliver wool is impregnated with this liquor, squeezed between rollers at 90% wet pickup, clamped by a pin frame to output width and reacted with dried for two minutes at 130 ⁰ C the aziridine derivative.

400 g of one of the water-soluble aziridine derivatives X or Y

AO9 88 6/14 _23/20

^; · ^Ζ · 29 993

are dissolved in 9, ^ 5 1 demineralized water and 50 g of the nonionic wetting agent described above are added. 10 1 equipment liquor is obtained which contains 40 g / l of the aziridine derivative. The aforementioned knit fabric is impregnated with the finishing bath, squeezed between rollers at 90% wet pickup, clamped by a pin frame to output width, and dried and reacted with the Aziridinderviat for 5 minutes at 130 ⁰ C.

To test the equipment fleet, these goods are washed together with an unfinished sample and ballast material in a drum washing machine with 2 g / l fine detergent at 40 ° C for 5 x 2 ° minutes, rinsing 5 times with cold water between each wash. The washed test specimens showed the following results:

Product % shrinkage in

Stitches- wales- wales-

direction direction

% Area shrinkage approx

Matting

without

19th - 10 7th - 4th 3 - 2 3 _ ■ * 3 _ ρ 8th _ C 7th - 5th 3 - 3 CX) - 5th 7th - 6 10.5 - 6 17th - 8th 15th - 9 14th - 11

27 11 5 6

5 13 12

13 13 16 23.5 22.5 25.5

4 to 5

4 to 5

4 to 5

3 to

3 to

4 to 5 3 to 4 3 to 4

1 to 2

The results show that the formula I corresponding products A to E and H to M provide good finishing effects. But as soon as the atomic ratio C: 0, as is the case with the products W, X and Y is the case, drops below 2.67: 1, practically no effect is achieved.

409886/1423

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O.Z.

29 ₉ 93

Example 2

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

Products B and X are each dissolved in perchlorethylene at a concentration of 50 g / l. Samples of the goods pretreated with sulfuric acid are impregnated with these solutions, these are pressed to a liquor pick-up of 100 % between rollers and the goods are then heated to 130 ^° C. for 15 minutes.

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

Product % shrinkage in

Stitch wale direction

% Area shrinkage approx

Matting

without

- 28

- 15

- 25th

- 24th

- 5th

- 25th

- 45.5

- 19.5

- 43.5

3 to 4 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 which contains 50 g / l of the product Z and 15 g / l MgCl ₂ · β HgO as a catalyst. The three samples are pressed to 90% liquor uptake and dried for 2 minutes at 130 ^° C. and reacted with the aziridine derivative. After testing according to the information in Example 1, the following results are obtained:

409886 / H23

/ 22

- 22 - - 10 G. fo area
Shrinkage 2334655 f> shrinkage in
Mesh-mesh
row sticks
direction direction - 3 - 27 Line 23 993 product - 19th - 5th - 7th Matting without - 4th - 10 - 12 1 P. _ 7 - 21.5 4 to 5 G - 13 3 to 4 Z 1 to 2

The values show that the products P and G as wool finishing agents are effective, while the product Z, which differs from P and G by the lack of polyether chains, is useless even though a catalyst has been added to support the reaction.

Example 4

A non-colored single jersey, 100 fo wool is with one of the impregnated products containing liquors mentioned below, squeezed off to a liquor pickup of 90%, stretched in a pin tenter at 90% of the raw material width and 15 f> overfeed 3 minutes at 130 ° C dried and reacted.

The following products are used:

Aziridine emulsion: 40 parts by weight of product B are added in the presence of 10 parts by weight of a polyaddition product which improves the emulsifiability of 58 moles of propylene oxide with 1 mole of polyethylene glycol with a molecular weight of 1800 to 2000 and 5 parts by weight of the wetting agent described below by adding 50 parts of water in portions at room temperature by stirring emulsified.

Polyacrylate I: 50% aqueous dispersion of a copolymer of 93 % n-butyl alcohol, 3 % acrylonitrile, 3 % N-methyl arylamide and 1 % acrylic acid.

Polyaorylate 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.

409886 / U23

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- 23 - O.Z. 29

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

Aminoplast I: 80 # strength aqueous paste of an N, N'-dimethylolurea etherified with methanol.

Aminoplast II: 50 # aqueous solution of N, N'-dimethylolethylene urea

Wetting agent: 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 b 'c d e f g

Aziridine emulsion
g / l 100 100 100 100 100 100 49 Polyacrylate I.
g / l 50 50 1 Polyacrylate II
g / l 50 Polyacrylate III
g / l 50 Aminoplast I.
g / l 10 10 10 Aminoplast II
g / l 20th Ammonium chloride
g / l 5 5 5 5 # Shrinkage (area) 45 16 14th 21st 21.5 18th Matting note 1 4th 4-5 3-4 3-4 4th

^ For sample b, the single jersey made of 100 % wool was treated with 2% of an adduct of 40 mol of ethylene oxide and 1 mol of castor oil, 5 % ammonium sulfate in water, pH 6.0, liquor ^{ratio 1:30, 90 minutes to 98 0} C heated (so-called blind coloring).

409886 / U23

- 24 - O.Z. 29 995

The wool material used here is so inert that it does not yet react with product B under the selected conditions reacts (see sample a in comparison to blank sample g) * If it is treated beforehand in the usual way for dyeing, then one can have perfect equipment without changing the other conditions (see sample b). Similar results are obtained through Use of an aminoplast, an acetalization catalyst and a dispersion of an acrylic ester forming polymer (see samples c to f).

Example 5

An off-white single jersey made of 100 <fo wool with 215 g / m weight per unit area is impregnated according to the recipes given in the table below with an aqueous solution at 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 J> minutes at ⁰

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%. Winding the product onto a roll, can be one hour dwell rolling and drying provided in a hot air rotary dryer (dryer) at an air temperature of 70 ⁰ C. The samples are Krumpfmarkierungen and in a drum washing machine 5 washes at 4O ⁰ C and 2 g / l subjected to a mild detergent. They are then allowed to dry without tension, the surface shrinkage that has occurred is read off and the felting is assessed as indicated above.

The following products are used:

Activator I; 70% solution of ammonium hydrogen sulfite / [NH ^) HS0.7, which was adjusted to a pH value of 4.5.

Activator II: 50 $ solution of sodium disulfite (Na ₂ S ₀ O ₁ -) with a pH of 4.5.

Activator III: 70 # solution of triethanolammonium hydrogen sulfite (OH-CH ₂ -CH ^ ΝΗ ^Φ HSO® with a pH of 4.5.

4 0 9 8 8 6/1423 / 25

- 25 - O.Z. 29 993

The wetting agent: Mixture of 50 parts of the tallow fatty acid ester of an adduct of 40 % ethylene oxide with polypropylene glycol with a molecular weight of 2500, 40 parts of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil and 10 parts of water.

Azridinemulsion: 40 parts by weight of the product B are mixed with 10 parts by weight of the adduct of 40 moles of propylene oxide and 1 mole of polyethylene glycol of molecular weight 2000 and 50 parts of water, 20 to 25 ⁰ C is added in portions with stirring. The emulsion contains 40 percent by weight of the aziridine derivative.

Pattern abc

Activator I (g / l) 50 -

Aktivabor II (g / l) - 135

Activator III (g / l) wetting agent (g / l) pH value

Liquor pick-up (#) drying in hot air for 3 minutes \ aziridine emulsion pH value

Liquor uptake {%)

Stay wet rolling at room temperature for 1 hour

The finishing samples a to c and an untreated sample d are sewn together and dyed in a single bath on a reel vat, wet, in a liquor ratio of 1:30 (based on the dry weight of the goods) for 90 minutes at 98 ^° C

1.5 % of the 1: 2 chromium complex of 4-chloro-2- \

- - 5 120 5 4.5 5 4.5 80 ' 4.5 80 80 130 ⁰ C 100 100 6.5-7 100 6.5-7 80 6.5-7 80 80

aminophenol-6-sulfonic acid * ■ 1-phenyl-

3-methylpyrazolone- (5)

5 %
pH 6.0

based on the dry weight of the goods

This is followed by rinsing with cold water, centrifuging and ^{drying for 50 minutes at 70 °} C. in a drum dryer with warm air. The equipment samples a, b and c are colored the same shade of red and show

409886/1423 ^{/ 2β}

- 26 - O.Z. 29 993

a clear mesh structure, while the pattern d in a lighter one It is colored red as patterns a to c and results in a blurred mesh structure with clearly discernible matting. the Samples are provided with a surface marking and subjected to the washing test.

5 heavy washes at 40 ° C with 3 g / l sodium dodecylbenzene sulfonate

template (fo) a b 5 C. 5 d Surface shrinkage β 7, 5 β, VJl 27 Matting 4.5 4, 4, 1 Example β

An off-white garbadine made of 100 % wool with a basis weight of 210 g / m 2 was padded with 50 g / l of activator I and 5 g / l wetting agent (both according to Example 5) at a pH of 4.5, on a liquor pick-up pressed from 50 % and treated wet thoroughly for 5 minutes with saturated steam on a decatizing machine and then suctioned off 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 made on the reel skid with 5 g / l of the aziridine emulsion according to Example 5 in water at a plot ratio of 1:50 for one hour run at room temperature and at pH 6.5 to 7, then drained the liquor, rinsed cold and colored (see below).

Sample b was padded with 80 g / l of the aziridine emulsion, pressed to 70% liquor uptake, left to roll for one hour at room temperature and dyed (see below).

Sample c was stained without further treatment.

For coloring, the 3 patterns were sewn together and placed on the reel skid in a plot ratio of 1:30 (based on the dry weight of the

409,886 / U ^23/2 7

O.Z. 29 993

Goods) 90 minutes at 98 ⁰ C colored with

1.5 % of the dye mentioned in Example 5

5 % (NH ₄ ) ₂ SO ₄
pH 6.0

based on Trο ckengewient the goods

Thereafter, cold rinsed and dried under low-tension fabric guide on a pin tenter for 2 minutes at 110 ⁰ C.

The samples a and b were colored a deeper red than the sample c. They showed a smooth surface image while that Pattern c was heavily creased.

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

The following shrinkage values were obtained: Sample a

% Area shrinkage
Surface image

- 6.5

smooth,

no

Matting

- 5.5

smooth,

no

Matting

- 24th

strong moiré effect, noticeable matting

The wet crease angles were measured on samples a to c before the washing test measured according to Tootal (see British patent specification 727 890). The following results were obtained:

template

Wet crease chain

Shot

a D. C. 78 107 113 119 148 168

As the sample a shows, the fabric pretreated with activator I takes up the product B even after the exhaust process.

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

/ 28

409886 / H23

233 ^ 655

- 28 - O. Z. 23

Example 7

A raw white double jersey made of 100% wool, weight per unit area

540 g / m 2, was pretreated with activator I 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 / l 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 filleting were obtained.

Untreated goods according to goods example

% Area shrinkage 24 8

Matting 1 4

Example 8

A top dyed single jersey 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 allowed to roll in foil for 24 hours at room temperature. It is then left to dry by laying out in the air, wrinkle marks are applied and it is washed five times in a drum washing machine at 40 ° C. with 3 g / l sodium dodecylbenzenesulfonate as detergent. After drying in air, the surface shrinkage is read and the felting is assessed.

The following results were obtained:

/ 29 A09886 / U23

- 29 - O.Z. 29 993

Sample a

Activator I (g / l) 30th - Wetting agent (g / l) 5 5 Aziridine emulsion (g / l) 90 - pH of the emulsion 5.5 5.5 Area shrinkage {%) 6.5 28.5 Matting 4.5 1

409886/1423. ^{/ 3} °

Claims (6)

Claims 1. Compound of the general formula I containing azirldine radicals 0 R, R ₁ ^C It t 3 »1 / XCCCN. ¹ '\ ^R 4 ^R 2 ^N CC' / η in the R ^ to Ry hydrogen atoms or low molecular weight Alkyl radicals, Q the radical of an n-valent alcohol or Phenol, η 2 or 3> X is a polyether chain made from butoxy and / or propoxy and optionally kthoxy units with a C: 0 atomic ratio of at least 2.67: 1 and a molecular weight of 150 to 1500 with η = 2 and of 150 to 3000 at η = 3. 2. Compounds containing aziridine radicals according to claim 1, characterized in that the molecule -XAX- consists of the divalent radical of a polytetrahydrofuran chain with a molecular weight of 1500 to 2500. 3. A method for reducing the running-in and matting of protein fibers containing or consisting of material by impregnation with a finishing bath containing at least one compound with several aziridine residues, and reaction of the aziridine residues with the protein, characterized in that there is at least one compound containing aziridine residues Fabric according to claim 1 or used. 4. The method according to claim 3 *, characterized in that the substance according to claim 1 or 2 is used in an aqueous emulsion together with a nonionic emulsifier. 5. The method according to claim 3 or 4, characterized in that the substance according to claim 1 or 2 is used in a finishing bath which has one or more, at least AO 9 8 86/1423/31 - 31 - O.Z. 29 2 containing N-methylol and / or N-methylol ether groups Substances, at least one acetalization catalyst and a dispersion of at least one film-forming acrylic ester polymer contains. 6. The method according to claim 3 or 4, characterized in that, to facilitate the reaction of the aziridine residues with the protein, the material to be finished is treated with a solution containing an inorganic or organic salt of sulfurous acid before or during the impregnation with the finishing bath, and lets the material treated in this way react with the salt of sulphurous acid BASF Aktiengesellschaft 409886/1423