DE2609206A1 - POLYMERIC COMPOUND, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR THE SHRINKAGE OF KERATIN FIBERS - Google Patents

Description

Applicant: IWS -NOMINEE COMPANY- LIMITED Wool House, Carlton Gardens, London SW 1, England

Polymeric compound, process for making it, and its use for shrinking keratinous fibers

The invention relates to polymeric compounds (polymers), which can react further, especially those polymeric compounds that are both anionic and cationic Groups contained in the molecule, processes for their production and their use in processes for treating keratin fibers (keratin-containing fibers) to make them shrink-proof (shrink-resistant) close,

Woolen fabrics can be treated either before or after dyeing by a chemical oxidative treatment, e.g. by chlorination, can be made shrink-proof (shrink-proof). As in However, with all degradation treatments, a high degree of washability can only be achieved at the expense of weakening the wool fiber will.

A high resistance to entanglement shrinkage without impairing the physical properties can thereby be achieved that you apply a prepolymer from an aqueous solution, but is a shrinkage making resin required, which is applied to a woolen fabric or wool

finooio / noil ORIGINAL INSPECTED

clothes from a concentrated fleet applied (from creature;) without the need for pre-chlorination.

Isocyanate-terminated Resins for Finishing (Applying) of woolen garments made from chlorinated hydrocarbon solvents are commercially available. Processes have already been described by which these products are emulsified and from concentrated fleets to wool garments (see British Patent 1,262,977). However, the emulsions are unstable because of the isocyanate groups react with water.

The free isocyanate groups of a urethane prepolymer rom Isocyanate-terminated polyether-type can be obtained according to the in British Patent 14-19306 "" Process can be reacted with sodium bisulfite to form an anionic product that blocked with bisulfite Contains isocyanate groups, according to the following equation:

R - NCO + HaHSQ ₅ > REHCOSO ^ Na ⁺ (1)

This water soluble compound is an effective means of securing woolen garments when after they shrink a dry padding process is applied. Since they are a Has anionic character, it behaves in the same way as an anionic wool dye and is made from concentrated Liquids exhausted under weakly acidic conditions on the fiber. Unlike a dye, the prepolymer diffuses however, due to its large molecule size, it is not in the fiber, but is restricted to the surface. So that Resin has a shrink-proofing effect> it should be cross-linked, what is best effected under alkaline conditions. As soon as the pH value of the exhausted (exhausted) liquor increases, the anionic resin is removed from the surface of the!, full faster desorbed than the blocked isocyanate groups can form urea crosslinks. The polymerization can then

* (corresponds to Australian patent application Kr. 8010/72)

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take place in the bath, which leads to a precipitate on the fabric and thus to a sticky feel (handle).

The compounds according to the invention are crosslinkable polymers which contain cationic groups, because of which they have an affinity for wool fibers. The preferred compounds result in stable, water-dispersible, amphoteric prepolymers, which together with dyes on a non-chlorinated wool fabric can be applied (exhausted), they have dye leveling properties and can after Application can be hardened to form a shrink-resistant (shrink-resistant) finish.

According to the invention, a polymeric compound contains at least a polymeric chain and cationic groups, containing at least two reactive groups per molecule, which can be crosslinked either directly or with a crosslinking agent; The networkable groups can be selected from the cationic groups "exist or they can be different and act non-ionized groups.

According to one aspect of the present invention, such a polymeric compound contains at least one polyether, Polyester, polyamide or polyurethane chain and at least two protonated amino groups.

The invention also relates to a method for treating Keratin fibers (fibers containing keratin) by applying the polymeric compound on the fibers from an aqueous bath and hardening (crosslinking) the compound with formaldehyde or a Substance that contains formaldehyde or releases formaldehyde, preferably under alkaline conditions.

According to a second and preferred aspect of the invention, a curable polymeric compound contains both anionic ones

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as well as cationic groups and the necessary crosslinkable groups "which are the anionic groups or the cationic groups or clearly non-ionized Groups can act.

The invention also provides a process for the preparation of curable polymeric compounds for treatment of keratin fibers, in the case of prepolymers, which are already may contain some of the required groups that are reacted to introduce anionic andA or cationic and / or crosslinkable groups, whereby a polymeric compound, which for the purposes of the present Invention contains required groups, either by introduction or in part by maintenance (Retention).

The invention also relates to a method for treating keratin fibers (keratin-containing fibers) by applying a hardenable compound according to the invention by exhaustion an aqueous bath and curing (crosslinking) the compound on the fibers «, the keratin treated by this method fibers that carry the cured (crosslinked) product of a compound according to the invention also fall into the Within the scope of the present invention.

The preferred polymeric chains in the compounds of the invention are polyether, polyester, polyamide or polyurethane chains, However, polyether chains are particularly preferred. They can easily be prepared by condensation of Alkylene oxides and a variety of prepolymers, .die contain such chains and by hydroxyl groups or by reactive groups such as thiol or isocyanate groups, are commercially available and can be used as starting materials for the preparation of the invention curable compounds can be used.

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The cationic groups in the compounds according to the invention can, for example, both the already mentioned protonated amino groups and acetidinium, pyridinium, Be isothiuronium and sulfonium groups. Phosphonium groups can also be effective, but they are difficult and expensive to manufacture. Some of these groups can themselves participate in the crosslinking reactions.

These groups can be bound in the most varied of ways and means in the polymeric chains or to the polymeric chains be, e.g. as follows:

Protonated amino groups -NH-, ®

Acetidinium groups -EK ^ J3HOH or N CHOH

© XJH ^ ^y ^ GH ^

Pyridinium groups / - -NH-COCH ₀ -N ^ A

Isothiuronium groups -NHCOCH ₉ -SC ^ ² ^

Sulfonium groups -NHCOCH ₂ -S- (CH ₂ CH ₂ OH)

The anionic groups, which are preferably also present, can be thiosulphate groups -SSO, "(Bünte salts) or carbamoylsulphonate groups -NHCOSO, ~ (bisulfite adducts of isocyanates be. These groups are both self-reactive and reactive crosslinkable under suitable conditions, but other cationic groups, such as carboxylic acid and sulfonic acid groups, can also be used. can be used provided that the Molecule other and crosslinkable groups are present.

It should be noted that in many cases the anionic or cationic groups are substituent groups, but this is not necessarily so and the charged groups can be part of the polymeric chain or backbone, as is the case, for example, with protonated nitrogen atoms. _/

There can also be non-charged, networkable groups and if only non-reactive cationic and anionic groups are present, they can use the entire crosslinking capacity, that is required for the production of a curable (crosslinkable) polymer. For examples such crosslinkable groups include isocyanate and thiol groups (the latter under alkaline conditions are weakly ionized).

The compounds according to the first aspect of the invention can be prepared by treating a solution of a compound which is at least ^ a polyether, polyester, polyamide or Polyurethane chain and containing at least two isocyanate groups, in an organic solvent with a strong Mineral acid.

The reactions in which isocyanates give rise to crosslinks in the presence of water can be expressed by the following equations (2) and (3) are shown:

ENGO + ■ H ₂ O > EMi ₂ + CO ₂ '(2)

+ EHCO> EKHCONHE (3)

It has now been found that prepolymers with terminal isocyanate react with concentrated mineral acids if they are dissolved in an organic liquid, with the formation of protonated amino groups according to the following Equation:

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EKE + H ₃ O ⁺ > EMH ⁺ ₃ + CO ₂ ¹ (4)

The protonated amino groups are not reactive towards isocyanate groups and a reaction similar to that according to equation (3) does not occur. It has been found that the number of charged amino groups formed is directly dependent on the amount of mineral acid used, 1 mole of sulfuric acid hydrolyzing 2 moles of isocyanate, including the conversion of all isocyanate groups. These products, which contain both free isocyanate groups and charged amino groups, have been found to be ^{stable over long periods of time under weak:} acidic conditions in the absence of water.

Suitable solvents for this reaction are those which both towards isocyanate groups and towards Mineral acids are relatively inert, such as ethyl acetate, acetone or dioxane. Suitable mineral acids include e.g. sulfuric acid, hydrochloric acid, orthophosphoric acid, Tungstic acid and fluorotitanic acid.

The conversion of the free isocyanate groups into charged amino groups gives the polyisocyanate a cationic character and these compounds have been found to exist over a wide pH range (e.g. from pH 2 to pH 11) Wool can be applied (exhausted) in contrast to the anionic bisulfite adducts, which are only acidic Conditions are noun. The rate of drawing increases as the number of amino groups increases. It can too Products containing both amino groups and free isocyanate groups for making wool shrink-proof by means of a scooping treatment can be used in this Palle however, as indicated above, there is a risk that crosslinking will occur in the bath, the tissues which are too sticky leads.

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The most advantageous of the protonated amino compounds contain no free isocyanate groups, are nouns to wool and can take part in a crosslinking reaction without being desorbed from the fiber surface. When all of the isocyanate groups in the prepolymer are converted to amino groups, the product is highly cationic and is easily absorbed by keratin. But even under alkaline conditions, this compound is not subject to any self-crosslinking. A S _c hrumpfbeständigkeit can be obtained when the alkaline treatment compartment in the presence of formaldehyde or a substance is performed, contains the formaldehyde or releases, such as a urea / formaldehyde or melamine / formaldehyde Harζ.

According to a further and preferred aspect, the present invention relates to a polymeric compound which contains at least one polyether (in particular a polyoxyalkylene), polyester, polyamide or polyurethane chain, ρ cationic groups and q anionic groups per molecule, where P + q is at least 2, and the molecule contains r crosslinkable groups, where r and ρ + q + r are both at least 2. If the cationic groups are reactive when crosslinked, then r ^ p. Similarly, if the anionic groups are reactive, then r ^ q. The average value for ρ (or q) can be any value above 0, but the values for ρ and q for each individual molecule are integral, ρ + q is preferably 3 and particularly preferably ρ has the value Λ and q the value 2.

Such a compound works within a wide range of pH values on full and can be hardened (crosslinked) on the wool under alkaline conditions.

The invention also relates to a method of treating Keratin fibers (fibers containing keratin) and the resulting ones treated fibers.

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Examples of crosslinkable groups that can be used in the preferred compounds are isocyanate bisulfite adducts -KECOSO ₂ "and Bünte salts -SSO _x " *. The latter can be introduced by reacting the Torlaufer compound with chloroacetic acid and treating with sodium thiosulphate to replace the Cl with -SSO ^ ". /

Compounds containing a group of the first-mentioned type can be prepared by a two-step process will:

a) by partial hydrolysis of the isocyanate groups of a polyisocyanate prepolymer with a mineral acid (according to equation (4)); and

b) by reacting the remaining isocyanate groups with sodium bisulfite to form the bisulfite adduct (corresponding to equation

For step (b) it is important that a homogeneous solution of the resin and sodium bisulfite is maintained by adjusting the proportions of water and water-miscible organic solvent as described in Belgian patent 795 575.

The final product has been found to be amphoteric because it has both amino groups that are active under neutral to acidic conditions are cationic, as well as isocyanate groups blocked by bisulfite, which are anionic. Experiments have shown that compounds of this type, which are made by polyisocyanate shrink-proof resins have been made over A broad pH value range can easily be applied to keratin fibers (can be applied or exhausted).

If the application is carried out at a pH of less than 6

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is performed, no crosslinking occurs in the bath, since the isocyanate groups blocked by bisulfite under acidic Conditions are stable. The crosslinking of the absorbed resin can be brought about by increasing the pH of the bath will. No desorption occurs under the alkaline conditions required for crosslinking Resin. Another advantage is that when a dye is applied to the wool at the same time as the resin (raised) ", the latter acts in a similar way to conventional amphoteric dyeing auxiliaries and uniform promotes (level), calm staining.

The ratio between the cationic and the anionic groups can be varied simply by using the for Promoting the amount of acid used by the reaction represented by the equation (4) changes. It is believed that all free isocyanate groups that remain after this stage react according to equation (1). Because it exists an optimal ratio of cationic to anionic groups, which both a good exhaustion (absorption) and also gives excellent shrinkage resistance, and this is found to be about 60:40. However, if the amount of protonated amino groups is increased, adding from formaldehyde or a formaldehyde source (a formaldehyde generator) to the bath, the optimal crosslinking is restored will.

Prepolymers with terminal polyisocyanate can also be used as Starting material for polymeric compounds with other cationic or anionic groups can be used. So can for example some or all of the terminal isocyanate groups be reacted with a halocarboxylic acid such as bromoacetic acid. The bromide obtained can with the most diverse Reagents are implemented as indicated below:

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With pyridine to form a pyridinite group

-NHCOCH ₀ Br + ff A - ^^ -irnnnfw. - Ψ \

β)

with thiourea to form an isothiuronium group

-NHCOCH ₀ Br + S = C ^ - ^ -NHCOCH ₀ -SC

² "^ iH ² '

Br with thiodiglycol to form a sulfonium group

/ CH ₀ CH ₀ OH ν © XH ₀ CH ₀ OH

-NiICOCH ₀ Br + S ^ ^d * - ^ -NHCOCH ₀ -S ^ ^ ^ ^d ^ CH ₀ CH ₀ OH ^ ^

with sodium sulfite to form a sulfonate group

-NHCOCH ₂ Br + Ua ₂ SO ₅ > -NHCOCH ₂ SO ₅ ^θ

Well ^@

with thioglycolic acid to form a carboxyl group

-NHCOCH ₂ Br + HSCH ₂ COOH ^ * ₂₂

Alternatively, some of the terminal isocyanate groups can be used or completely hydrolyzed to amino groups and the amino groups can be reacted with epichlorohydrin and alkali are formed with the formation of Acetäiniumgruppen according to the equation

-NCO> -NHp ^ - NH CHOH

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The partial reaction with a reagent can lead to a partial substitution of the available centers by a specific cationic or anionic group and the subsequent reaction with > another reagent can lead to a partial or complete substitution of the remaining centers by another group, each anionic or is cationic, lead. The selection of the appropriate reaction conditions and the stoichiometric amounts can depend on the T? achmanne can also be made readily with reference to the examples below.

Another type ^of: cross-linkable group which may be used in the inventive compounds is the thiol group. Since thiol groups are weakly ionized in alkaline solution, they give a compound in which they occur together with cationic groups a weakly amphoteric character. In addition, the thiol groups in an existing prepolymer can be used in reactions to introduce other, cationic: "or anionic, groups, and the remaining thiol groups can provide the necessary crosslinking capacity.

For example, a diisocyanate can be partially hydrolyzed by mineral acid to form a protonated one Amino group and the remaining isocyanate group can be with a Thiol group are reacted on the prepolymer in order to bind the cationic amino group to the prepolymer.

It has been found that the effectiveness of amphoteric compounds according to the invention in terms of preventing Shrinkage of woolen textiles during washing with the ratio of cationic to anionic groups in the polymer varies. This ratio should preferably be within the range of 4-5: 55 "to 6-35", with most preferred ratio is about 60:40. If less than

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40 % cationic groups, the absorption (scooping up) is considerably reduced, while with more than 70 % cationic groups the polymer cannot be easily distributed on non-chlorinated wool to form the film which is necessary for effective shrink-proofing.

The accompanying drawing shows a diagram in which the surface area after washing for 3 hours is plotted against the ratio of cationic to anionic groups (expressed in % cationic groups) for a trifunctional isocyanate made from a polyether triol with a molecular weight of 3000 ^: and hexamethylene diisocyanate has been prepared in which the cationic groups are formed by acid hydrolysis of the isocyanate to protonated amino groups. It appears, however, that the change in potency with the ratio of cationic to anionic groups is essentially similar for all amphoteric polymers which are crosslinkable, and with the most varied combinations of groups in the preferred ratio as indicated below obtained satisfactory results.

Examples of polyether chains which can occur in the compounds according to the invention are: polyoxyethylene, polyoxypropylene and (because of their excellent lightfastness) in particular polytetramethylene oxide chains. The term "polyether" used here also includes polythioethers, such as, for example, the condensate products of thiodiglycol. Examples of polyester chains include polyester chains obtained by reacting dicarboxylic acids such as adipic acid, malic acid, terephthalic acid, sebacic acid, malonic acid and itaconic acid with diols such as hexanediol, ethylene glycol, or diols of the OH- (C ₁₁₁ H ₂₁₁₁ O) _n -H , in which m is the number 1 to 12 and η is the number 1 to 50, have been prepared.

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It has been found that crosslinkable compounds based on polyether (polyoxyalkylene) chains improve lightfastness the shrink-proof finish (surface condition) on keratin fibers is greatly improved if the alkylene groups in the Polyether chains, unbranched carbon chains with 3 or preferably have 4 or more carbon atoms, i.e. when the poly (oxyalkylene) chains have the formula

- - C (CH ^ O ^ -

wherein m has a value of at least 3 and preferably of 4, and η has a value of at least 1, provided that if η = 1, m = at least 10.

Although the present invention is useful in terms of its utility is not dependent on any particular theory, it is believed that the presence of chains in the alkylene groups as in the customary oxyalkylene polymers are present, which consist of Propylene or butylene oxide can be produced at a lighter weight The chains break when exposed to light, which also occurs with the very short ethylene chain.

Polyamide chains that may be present include e.g. Polyhexamethylene adipamide and polycaprolactam chains as well also chains of the type:

Polyurethane chains that can be used include, for example, those made by reacting diisocyanates such as hexane ethylene diisocyanate (HLiDI) or toluene diisocyanate (TDI) with a diol as indicated above.

Examples of suitable isocyanate prepolymers for use in the production of amphoteric resins are those which contain at least two isocyanate groups per molecule,

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and preferably those with a molecular weight of at least 500. These can be:

1.) the result of the joint reaction of simple isocyanates with, for example, water, itself or other isocyanates, such as Desmodur Ή (Bayer), which is produced by reacting 3 moles of hexamethylene diisocyanate with 1 mole of water;

2.) prepolymers, the implementation of more than one active hydrogen atom-containing compound with a appropriate number of moles of the diisocyanate are formed. Suitable compounds include polyols, polyamines, polyamides, Polycarboxylic acids, polythiols, polybutadienes terminated with hydroxyl or carboxyl, silicones terminated with ' Hydroxyl or amino. These connections can also be:

a) Polyethers, e.g. those obtained by polymerizing Ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide are obtained, -or their copolymer is at ions or Graft polymerization products, or those obtained by condensation or alkoxylation of polyhydroxy alcohols will;

b) Polythioethers, e.g. those used in the condensation of Thiodiglycol with itself and / or with other glycols Dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols are formed;

c) Polyesters, e.g. those derived from polybasic saturated or unsaturated carboxylic acids (or Carboxylic acid anhydrides) and polyvalent saturated or unsaturated alcohols, amino alcohols, diamines, polyamines or mixtures thereof, or polyesters of lactones, "like caprolactone;

d) polycarbonates and

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e) natural oils such as castor oil.

Examples of polyisocyanates which are suitable for the reaction with the compounds given above are the following: aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cycloaliphatic Diisocyanates such as cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 2,4- and 2,6-hexahydrotoluylene diisocyanate, araliphatic diisocyanates such as p-xylylene diisocyanate, aromatic diisocyanates, such as p-phenylene diisocyanate, 1-chloromethylphenyl-i, 4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, Dimer acid diisocyanates, 2,4- or 2,6-tolylenediiso cyanate.

A preferred compound according to the invention with a polyamide chain and anionic -SSCU ~ groups can, for example, consist of a commercially available shrink-resistant resin (Hercosett 57) which have a polyamide chain and pendant acetidinium ions

and / or IT-chlorohydrin groups

-F-CH ₂
CHOH
CH ₂ Cl

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-V-

This resin can be treated with a solution of a water-soluble thiosulfate to remove some or all of the Cl groups to be replaced by ionic -SSOv "groups below Formation of a resin with protonated (tertiary) amino groups and anionic Bünte salt groups.

Another and particularly preferred type of compounds according to the invention can be prepared from prepolymers which contain one or more polyether chains which are connected and / or terminated with dicarboxylic acid residues, of which at least two contain crosslinkable substituent groups. ^:

These prepolymers can be prepared by reacting polyether diols with functionally substituted dicarboxylic acids, the molar ratio between the diol and the acid determining the number of functional groups per molecule, and such compounds are described in German Offenlegungsschrift No. 2 "4-36 035. They can are reacted to introduce v ^ on cationic or anionic groups, for example, the dicarboxylic acid corresponding to the general formula

R "0 E"

HOOC-E '-COO- [ (^ 2ιά ^Ο \ ~ ^Ο ~ ^ ' ~ ^G00] x " ^H

where E is a trivalent organic Eest, R "is a crosslinkable or a cationic group or contains one, χ a value of at least 2, η a value of at least 1 and (C E o) mean a straight-chain oxyalkylene group, in which m has a value of at least 3, and if η = 1, m has a value of at least 10, with the proviso that the molecule has at least one cationic Eest E "and at least contains two networkable Eeste E "(which do not have to be mutually exclusive).

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A particularly preferred "connection is made by. Implementation of four moles of a thiolic acid, such as thio malic acid, with 3 moles of a poly (tetramethylene oxide) and then Implementation of at least one thiol group per molecule with one A compound containing a cationic group such as a diisocyanate in which an isocyanate group becomes a Amino group has been hydrolyzed.

The preferred compounds according to the invention form particular effective anti-shrink resins for keratin fibers. to Keratin fibers that can be treated according to the invention, include e.g. Kashmir., Vicunja, Mohair, Hair, Llama, and in particular Wool. The pasers can be in the form of loose stacks, lace, roving, yarn or woven, non-woven or knitted fabrics.

The treatment can be carried out in conventional textile equipment be carried out and an advantage of the compounds according to the invention consists in that they entjä from concentrated liquor which is attached to wool without subjecting the wool to an oxidative pretreatment, such as chlorination got to. In addition, the preferred compounds, which are applied under acidic conditions, can be in the dyebath before, after or at the same time as the staining, they have the advantage that they are uniform in staining support financially. In the latter case, it may be necessary to use a conventional dye leveling agent.

All classes of anionic dyes normally used for dyeing wool can be used, can be used: e.g. acidic leveling, acidic vTalk, 1: 1 pre-metallized, 1: 2 pre-metallized chromium and reactive dyes.

When applying the compounds to wool, the pH of the treatment bath can be varied widely, in particular from

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pH 2 to pH 11. For the majority of amphoteric polymers, however, it is preferred to have a liquor pH of 2 to 6 to be used because the polymer is stable under weakly acidic conditions. Inorganic salts such as sodium sulfate, sodium chloride and ammonium sulfate, support the absorption (scooping out). It has been found that certain wetting agents, like Aerosol OT- (Cyanamid), Lissapol N (ICI) and Silicone L77 (Union Carbide) ^ the uniform pulling (scooping up) support financially.

However, some polymers, such as those that have thiol groups as crosslinkable groups, can be used in weak alkaline solution, for example at pH 7 to 9, applied will.

A wide range of application temperatures can be used. For some compounds, room temperature may be appropriate, but for most compounds it is preferred to apply them at elevated temperatures up to and including the boiling temperature. In a frequently preferred method, the temperature of the bath is slowly increased from 25 ° C. The scooping up (scooping out) is usually finished when the temperature reaches 70 to 80 ⁰ G, but heating can be continued until boiling.

Once the prepolymer has been applied to the roll, it can be crosslinked to form the resin product to complete. By dry heating or by increasing the pH of the bath to a value above pH 7 »5, hardening can be brought about as the overwhelming majority of the crosslinkable used according to the invention cationic or anionic groups is curable under alkaline conditions. The hardening (cross-linking) in an alkaline bath takes place at any temperature above ambient temperature, the speed with the

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Temperature increases. Particularly advantageous conditions are because this is often used for the treatment of some classes of Eeaktivfarbstoffen 10 minutes at 70 ⁰ G and pH 8.5. Curing by dry heating, which can be used for example with thiol groups, can be combined with drying the treated fibers after they have been removed from the treatment bath.

Although the "utility of the present invention in is in no way dependent on any theory or mode of operation, it is believed that using compounds with amino and bisulfite adduct groups deprotonation of the amino groups occurs, which is followed by a reaction with the isocyanates blocked with bisulfite according to the following equations (5) and (6):

R - UH® ₃ 22-> ENH ₂ + H ₂ O (5)

E - M ₀ + EHHCOSO, - Na®> ERECOlfflE + NaHSO ^ (6)

Under alkaline conditions, the bisulfite adduct des Isocyanate can be easily deblocked (inverse of equation (1)) and it can then easily be according to the equations (2) and (3) are implemented. In both cases the product is a substituted urea.

The curing (crosslinking) of the other crosslinkable groups or combinations of groups takes place according to mechanisms such as they occur in the sails of such groups, e.g. when thiol compounds harden (crosslink) during formation of disulfite bonds.

Another advantage of these resins is that they give the fabrics a smooth-drying finish (surface texture) can lend. It is therefore possible to apply

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a exhaustion process instead of a padding process to produce non-iron fabrics.

The invention is illustrated in more detail by the following examples, but without being limited to it.

example 1

A trifunctional isocyanate prepared from a polyether triol with a molecular weight of 3000 and HMDI (Synthappret LKF) (125 g of an 80% solution in ethyl acetate, supplied by Bayer) was diluted with 20 g of ethyl acetate. The solution was stirred while 3 g of sulfuric acid mixed with 10 g of ethyl acetate was slowly added. After the final addition, stirring was continued for an additional 30 minutes. 160 g of isopropanol were added to this mixture, then a solution of 10 g of sodium metabisulphite in 60 g of water was added. Stirring was continued until the infrared spectrum indicated the disappearance of the characteristic isocyanate maximum at 2280 cm " ¹ (usually overnight). The product was a water-clear solution with a solids content of 35% and a molar ratio of cationic to anionic groups, determined by filtration, from 60:40.

The product obtained in the above process (1.4 g of a 35% solution) was mixed with 0.16 g of a wetting agent (Aerosol OT75 from Union Carbide) and then diluted with V / a water from 25 ° C. to 300 ml. Acetic acid was added to adjust the pH to 4 to 5. 10 g of a previously wetted sample of a woolen fabric (cf. Table I below) were immersed in the treatment liquid (liquor) and then in a solution of 2 g of anhydrous sodium sulfate in water. The temperature was increased at a rate of 2 to 4 ^° C. per minute to boiling with occasional stirring. The liquid (liquor) was

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gradually clear as the resin has been applied (scooped out) to the fabric. Boiling was continued for 5 minutes, after which the liquid was cooled to 70 to 80 ⁰ C. The pH of the bath was adjusted to 8 to 9 and the temperature was kept I5 minutes at 70 to 8O ⁰ C. The tissue was extracted with water, dried at 100 G for 20 minutes and then semidecatized for 3 minutes in steam and 1 minute in vacuo. The feel (handle] was excellent The following Table I shows the different in this process for fabrics which have been tested by washing in Einei 15 l-Cubex-washing machine, Antiverfilzungseffekt ^achieved.:.

examined tissue

Table I.

% Area shrinkage after washing for 3 hours

untreated treated with 5 % resin

Serge fabric 64-2

Line flannel fabric

(unbleached) 62 0

Single jersey fabric

(28/28 yarn up to one

Coverage factor of 1.1) 70 3

Single jersey fabric (Shetland) 65 2

Example 2

1.7 g of the product of Example 1 were mixed with 0.2 g of Aerosol OT75 and diluted to 300 ml with water. These were 2 g previously dissolved sodium sulfate and acetic acid up to a pH of 4-5 are added. The fabric (see the following Table II) was in this liquid for 10 minutes at 35 ° C (Liquor) and then a wool dye solution (8 reactive dyes, a pair of one 1: 1 pre-metallized dye and a 1: 2 pre-metallized dye

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Dye as indicated in Table II below) was added while the temperature was slowly increased to 70 ° G at a rate of 2 ° C per minute and held at that temperature for 15 minutes. The temperature was then slowly raised to the boiling point and held at that temperature for 20 minutes. After cooling to 70 to 8O ⁰ C, the pH of the bath was adjusted to 8.5 by adding sodium carbonate to the ninth After a further I5 minutes, the sample was extracted with water, 20 minutes at 10O ⁰ C and dried for 3 minutes in steam for 1 minute semi deka advantage in vacuo.

The feel (feel) of the fabric was excellent, and the staining was even (no matter) and calm by comparison to similar staining done in the absence of any leveling agent. The matting resistance was determined by washing tests similar to those described in Example 1.

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- 24 - 26Ü9206 Λ Chemicals) with the mix Table II 2 2,6-tolylene diisocyanate Dye fabric Area shrinkage
after washing in% 3 salary 1 hour 3 hours 2 would have. Drimalan Brilliant Blue
F2RL (Sandoz) Serge- ^ tissue 0 2 "unbleached
Dash flannel
tissue 2 2 "Single jersey
tissue 1 3 Drimalan Red F2GL unbleached
(Sandoz) ^: dash flannel
tissue 1 -2 Drimalan Blue F2GL
(Sandoz) " 2. 0 Lanasol Red 6G (CI.
Reactive Red 84) " 3 0 Lanasol Blue 3 & (CI.
Reactive Blue 69) " 3 Procion Turquoise Blue HA
(CI.Reactive Blue VO Serge fabric 0 was produced Neolan Flavine GFE (CI.
Acid Yellow 103) (2 parts)
Neolan Navy-blue 2RLG
(Ciba Geigy) (1 part) 0 with a molecular Irgalan Gray BL
(Ciba-Geigy) 1 weight of 3000 (Polvurax G3OOO from B.P. Example 3 46 g of an 80:20 mixture of 2,4- and An isocyanate-terminated prepolymer (Suprasec EN from I.C.I.) until the by converting 500 g of a triol in free isocyanate decreased by 50%

603838/0977

26U9206

To a solution of this product (25 g solids) in ethyl acetate (100 g) was added "Synthappret IjKF" (62.5% of the commercially available 80% product). The mixture was refluxed for 45 minutes. After cooling to room temperature, a solution of 1 g of concentrated sulfuric acid in Ί0 g of ethyl acetate was added over a period of 10 minutes with stirring, then stirring was continued for 30 minutes after the first addition. 200 g of isopropanol were added, then a solution of 6 g of sodium metabisulfite in 20 g of water was added. This homogeneous mixture was stirred overnight until a clear solution with a resin solids content of 21 % was obtained.

The product (4 % resin solids based on fabric weight (owf)) along with 1 % owf Drimalan-Brilliant Blue 2RL as indicated in Example 2 was applied to a WoIl-Serge fabric. The fabric was dyed evenly and after 3 hours of washing had a surface felting shrinkage of "- only 3% compared to 64% for an untreated sample.

Example 4

In the case of a combined dye-resin scooping treatment, the resin is usually fully scooped up before the dye (upset). The prepolymer can, if preferred is, have been hardened (crosslinked) in some stage after scooping out (application) and this does not necessarily have to be be at the end of the treatment sequence.

In an example illustrating this process, 1.4 g of the product of Example 1 mixed with 0.16 g of Aerosol OT75 and then diluted to 300 ml with water at 25 ° G. Up to acetic acid was added to pH 4. A previously wetted sample of a single wool jersey fabric (10 g) was poured into the treatment liquid and then into a

838/0917

-26- 2o (J 9

Solution of 0.2 g of anhydrous sodium sulfate immersed in water. Then, 0.1 g Xylene Fast Blue P were (CI. Acid Blue 82), which had been previously dissolved in water was added and the temperature was raised at a .Geschwindigkeit from 2 "to 4 ° G per minute under continuous stirring to 80 ⁰ C then held at that value for 20 minutes, after which the resin was exhausted (applied), the bath was adjusted to pH 8.5-9 by the addition of ammonium hydroxide and stirring continued for 15 minutes, then formic acid was added was added to bring the pH to 3 and heating was continued to boiling point After boiling for 20 minutes, the fabric was rinsed with water, dried and semidecatized.

The fabric was evenly dyed and had a surface entanglement shrinkage after washing for 3 hours of only 5 % compared to that of an untreated sample of 65 %.

Example 5

120 g of a difunctional isocyanate prepolymer based on of a polybutylene oxide diol (Adiprene LS from Dupont) were dissolved in 100 g of ethyl acetate and a solution of 9 * 8 g concentrated sulfuric acid in 25 g of ethyl acetate were slow and added carefully with stirring. After the final addition, stirring was continued for an additional 30 minutes. The product was diluted with isopropanol and a solution of 12 g of sodium metab sulfide in 50 g of water was added. Stirring was continued until the IR spectrum disappeared the isocyanate maximum at 2280 cm. Water or isopropanol was added as required to to maintain a homogeneous solution during the reaction. The final product had a resin solids content of 20%.

A sample of this product (5 % resin solids owf) was made

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-27- 26U9206

together with 1% owf Drimalan Brilliant Blue 2EL applied to a wool serge fabric (exhausted), as indicated in Example 1. After washing for 1 hour, as in Example 1, the treated fabric showed a surface felting shrinkage of 0 %.

Example 6

13.4 g of trimethylol propane were reacted with 360 g Adiprene LS 570 for 5 hours under stirring and heating to 150 ⁰ C. The reaction was then ended because the free isocyanate content had fallen by 50%. This product (20 g) was dissolved in 50 g of ethyl acetate and a solution of 0.4-5 g of concentrated sulfuric acid in 5 g of ethyl acetate was slowly added with stirring, and after the final addition, stirring was continued for 45 minutes. Then 100 g of isopropanol were added and then a solution of 4 g of sodium metabisulphite in 20 g of water was added. More water was added until a clear solution was obtained. Stirring was continued throughout the night. The product had a resin solids content of 15 %.

A sample of the above material (5% o.w.f.) together with Drimalan Brilliant Blue 2RL (1% o.w.f.) as indicated in Example 1 applied to a wool serge fabric (exhausted).

Example 7

This example was carried out in the same way as in example 2, but this time using 1 % owf Silicone L77 (from Union Carbide) as the wetting agent instead of Aerosol OT. The staining was even and calm and the fabric shrank by only 2 % after washing for 3 hours compared to a shrinkage of 64% for an untreated sample.

■ 6038 38 / Ό377

Example 8

As indicated in Example T, 10 g of sulfuric acid were reacted with 125 S Synthappret LKF. This amount of acid was sufficient to convert all of the free isocyanate groups into protonated amino groups. ,

A sample of this product (0.5 g resin solids) was diluted to 30 ml with water and a 10 g sample of serge fabric was wetted in the liquid. - The pH was adjusted to 6 to 7. There were 2 g of previously dissolved sodium sulf; added and the temperature was slowly raised to 80 ⁰ C. At this point the liquid was completely clear. The pH was adjusted to 8.5 to 9 and a formaldehyde solution (1 g of 4-0% formaldehyde, diluted with 10 ml of water) was added with stirring. After 15 minutes at 80 ° C., the sample was removed and dried. The shrinkage results for this and similar examples with other hardening agents (crosslinking agents) ^'V are given in the following Table III.

Table III Fabrics - Undyed Serge Fabric (5 % Resin owf)

Hardening agent (crosslinking agent)

Area shrinkage in% after washing for 3 hours in one Cubex washing machine

a) formaldehyde (4- % owf)

b) Urea / formaldehyde precondensate (BT6) (5 % owf)

c) ethylene urea / formaldehyde (BT 324-) (5 % owf)

d) melamine / formaldehyde modified with ethylene urea (BT 328) (5 % owf)

e) methylated melamine / formaldehyde (BT 329) (5 % owf)

O.

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f) partially polymerizes urine ff / -

Formaldehyde (BT 336) (5% o.w.f.) O

The hardening agents (crosslinking agents) (b) to (f) are from from BIP Chemicals Limited.

Example 9

A sample (0.1 g resin solids) of the product of Example 1 was mixed with 0.03 g Aerosol OT and then diluted to 400 ml ^{with water at 40 ° C.} A wool flannel fabric (10 g) was wetted in this solution and stirred for 5 minutes. 1 g of a previously diluted dispersion of a 50% strength acrylate polymer (Rohm & Haas N485) was slowly added with stirring. The pH was adjusted to 4 and the bath was slowly ^{heated to 80 °} C., at which point the exhaustion was complete. The sample was then aftertreated at pH 9 and 70 ^° C. for 10 minutes and then ^{dried for 10 minutes at 120 °} C. and pressed with steam for 3 minutes.

After washing the sample for 1 hour, its surface shrank 3% compared to 54% for an untreated sample from the same tissue.

The polymers used in Examples 10 to 21 below were made from Synthappret LKF (Bayer). This compound was the reaction product of a polyether triol with hexamethylene diisocyanate (molecular weight 3000 to 3500). Similar compounds can, however, be obtained from products with different backbones to those with other isocyanates (both aromatic and aliphatic) are completed getting produced. In all of the following examples the ratio of cationic groups to anionic groups was about 60:40.

809838/0977

Example 10 (sulfonium and carboxyl groups)

Synthappret IKF (11.5% solids) was reacted with 1.42 g of bromoacetic acid until all isocyanate groups had reacted. The product was dissolved in a mixture of 50 g of isopropanol (I PA) and 25 g of water. 0.83 g of thiodiglycol were added and the mixture was ^{stirred at 50 °} C. for 3 hours. 0.3 g of thioglycolic acid were then added and stirring was ^{continued at 70 °} C. for 3 hours.

The product (5 % owf) was applied (scooped) to a washed woolen fabric in the presence of Glauber's salt (10 % owf) at pH 4 to 5 (acetic acid) and a liquor ratio of 50: 1. The temperature of the liquid (liquor) was increased to 80 ^° C., at which point the application (scooping out) had ended. The pH of the liquid was adjusted to 8 to 9 and the temperature was held at 70 ° C for 10 minutes. The sample was removed from the bath, rinsed with water, extracted with water and dried for 30 minutes at 10O ⁰ C 'before a wash test was subjected to 3 hours as indicated above. The following results were obtained:

Area shrinkage in %
treated 1 %
untreated 68 ^

Example 11 (pyridinium and carboxyl groups)

Synthappret IJCF was reacted with bromoacetic acid and the product obtained was dissolved in I PA / water as indicated in Example 10. 0.54 g of pyridine were added and the mixture was ^{stirred at 50 °} C. for 3 hours. 0.31 g of thioglycolic acid were then added and stirring was ^{continued at 70 °} C. for 3 hours.

8Ö983S / 0377

The product was applied (exhausted) to a woolen fabric, cured (crosslinked), dried and examined as in Example 10 for its shrinkage strength. The area shrinkage after washing for 3 hours was 1 %,

Example 12 (sulfonium and sulfonium acid groups)

Synthappret LKF was reacted with bromoacetic acid and that
The product obtained in this way was dissolved in I PA / water as in Example 10. 0.83 g of thiodiglycol was added and the mixture was heated to 70 ° C. for 3 hours. Then, 0.4-3 g of sodium sulfate were added and the solution was heated to 70 ⁰ C for 3 hours.

The product was applied to a woolen fabric, crosslinked, dried and, as in Example 10, for its shrinkage resistance examined. The area shrinkage after washing for 3 hours was 0%.

Example 13 (pyridinium and sulfonic acid groups)

Synthappret LKF was reacted as in Example 10 with bromoacetic acid and then with pyridine. About the product obtained 0.43 g of sodium sulfite dissolved in 5 g of water were added. The solution was heated to 70 ° C for 3 hours.

The product obtained in this way was applied to a woolen fabric and crosslinked as "in Example 10, and then the treated fabric, after washing for 3 hours as above, had an area shrinkage of 0 % .

Example 14 (isothiuronium and carboxyl groups)

Synthappret was reacted with bromoacetic acid as in Example 10 and then dissolved in I PA / water. There was 0.44 g of thiourea added and the solution was left on for 3 hours

609838/0977

50 ⁰ C heated. Then 0.31 g of thioglycolic acid was added and heating was continued for 5 hours at 70 ° C.

The product obtained (5% owf) was applied to a woolen fabric while boiling (scooped out) and cured (crosslinked) as in Example 10. The area shrinkage after a 3-hour washing test was 0 %.

Example 15 "(isothiuronium and sulphonic acid groups)

Synthappret LKE ¹ was reacted with bromoacetic acid and then with thiourea as in Example 14. There are 0.4-3 g sodium sulfite, dissolved in 10 g of water was added and the solution was heated to 70 ⁰ G 5 hours.

The product (5% o.w.f.) was applied to a woolen fabric and crosslinked and tested as in Example 10. The area shrinkage after the washing test was 0%.

Example 16 (acetidinium / carboxyl groups)

Synthappret IjKI (11.5% solids) was dissolved in 20 g of ethyl acetate and, with stirring, 0.33 g of sulfuric acid dissolved in 5 g of ethyl acetate was slowly added. After the evolution of carbon dioxide had ceased, 0.48 g of dried bromoacetic acid was added. The mixture was gone. 50 g of isopropanol, 25 g of water and 0.63 g of epichlorohydrin were added and the pH was adjusted to 7 to 8 with sodium carbonate. The mixture was heated for 15 minutes at 70 ⁰ G. Then 0.51 g of thioglycolic acid was added and heating was continued for 3 hours at 70 ° C.

The product obtained was applied to a woolen fabric and cured (crosslinked) and tested as described in Example 10. The area shrinkage after washing for 3 hours was 2 %.

609838/0977

Example I7 (Acetidinium / Carbamoylsulfonate Groups)

Two thirds of the isocyanate groups of the Synthappret LKF (11.5 s) were hydrolyzed by reaction with sulfuric acid as indicated in Example 16. The product was dissolved in 50 S isopropanol and 25 g of water and a solution of 0.6 g of sodium metabisulfite in 10 g of water was added. The pH of the solution was adjusted to 6 with a sodium sulfite solution, and it was stirred for 1 hour at room temperature. There were added 0.63 g of epichlorohydrin, and the mixture was heated at 6O ⁰ C for 15 minutes. The product obtained in this way (0.5 g solids) was dissolved in 1 g isopropanol and then mixed with a wetting agent (1.6 g of a 10% strength Aerosol OT solution in IPA). This mixture was applied to woolen fabric in the presence of 10 % owf sodium sulfate at a pH of 4 to 5 and cured (crosslinked) as indicated in Example 10. The area shrinkage after washing for 3 hours was 2 %.

Example 18 (pyridinium / carbamoyl sulfonate groups)

11.5 g of Synthappret LKF were partially reacted with 0.95 g of dried bromoacetic acid by heating at 70 ° C. in 10 g of ethyl acetate for 4 hours. The product obtained in this way was dissolved in 50 g of isopropanol. A solution of 0.5 g of sodium metabisulphite in 5 g of water was added to this. The pH was adjusted to 6 by adding sodium sulfite. After 1 hour, 0,54- g of pyridine were added and the solution was stirred at 4-0 ⁰ C 4 hours.

The product (5 % owf) was applied to a woolen fabric and cured (crosslinked) as indicated in Example 10. The area shrinkage after washing for 3 hours was 2 %.

609838/0977

Example 19 (pyridinium / Bünte salt groups)

Synthappret LKF (11.5 S solids) was made through. Heating at 70 ° C. for 4 hours reacted with 1.4-2 ', g of dried bromoacetic acid. 50 g of isopropanol and 25 g of water were added to this. After the addition of 0,54-, g of pyridine, the solution was heated for 2 hours at 50 ⁰ C. Then 0,54- g Eatriumthiosulfat were added and heating was continued at 6O ⁰ C for 5 hours.

The product (5 % owf) was applied (scooped) to a woolen fabric and cured (crosslinked) as in Example 10. The area shrinkage after washing for 3 hours was 3%.

Example 20 (sulfonium and Bünte salt groups)

Synthappret LKF was reacted with bromoacetic acid as indicated in Example 10. 0.83 g of thioglycol were added to the product thus obtained, dissolved in 50 g of isopropanol and 25 g of water. After heating at 50 ° C. for 2 hours, 0.54 g of sodium thiosulfate was added. The heating was ^{continued at 60 °} C. for 2 hours.

The product was applied to a woolen fabric and cured (crosslinked) as indicated in Example 10. The area shrinkage after 3 hours of Yfaschen was 0%.

Example 21 (sulfonium and carbamoyl sulfonate groups)

11.5 g of Synthappret LICF were reacted with 0.95 g of bromoacetic acid and the product obtained was dissolved in IPA / water, as indicated in Example 18. To. a solution of 0.5 g of sodium metabisulphite in 5 g of water was added to this solution. After 1 hour, 0.83 g thiodiglycol were added and the temperature was raised to 4-0 ⁰ C 4-5 minutes.

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26U9206

The product (5% o.w.f.) was applied to a woolen fabric and cured (crosslinked) as indicated in Example 17. the Area shrinkage after washing for 3 hours was 0%.

Examples 22 to 24 given below are used other prepolymers for producing the η according to the invention amphoteric polymers used.

The Helastic LV used in Example 22 was an aromatic analogue of Synthappret IiKF which by reacting a similar polyether thiol with toluene diisocyanate was produced. In Examples 23 and 24, the polymers were made from prepolymers with a terminal Thiol produced. By reaction of at least one of the Thiol groups with a derivative of a diisocyanate in which one of the isocyanate groups was hydrolyzed with mineral acid, cationic protonated amino groups were introduced.

Example 22

To 34 g of Helastic LV dissolved in 20 g of ethyl acetate was added slowly a solution of 0.74 g of sulfuric acid in 10 g of ethyl acetate was added with stirring. After 30 minutes the product was in 100 g of isopropanol and 20 g of water were dissolved and a solution of 3 g of liatrium bisulfite in 15 g of water and 0.5 g of triethylamine was added admitted. Stirring was continued for 2 hours.

The product (5 % owf) was applied (scooped) to a woolen fabric and cured (crosslinked) as in Example 17. The area shrinkage after washing for 3 hours was 2 %.

609838/0977

Example 23

To a solution of 2.5 g of dicyclohexylmethane diisocyanate (Hylene W from Dupont) in 50 g of ethyl acetate, a solution of 0.5 g of sulfuric acid in 10 g of ethyl acetate was slowly added with stirring. The product was dissolved in 25 g of toluene together with a thiol-terminated polyether triol with a molecular weight of 3000 to 3500 (Oligan from Ciba-Geigy). There were added 2 g of triethylamine, and the mixture was heated to 60 ⁰ G 45 minutes.

The product (0.5 g solids) emulsified with an equal weight amount of an emulsifying agent (Lissapol NX from IGI) was applied to a 10 g single jersey fabric in the presence of 0.5 g sodium sulfate at pH Value of 7 to 8 was applied while increasing the bath temperature to 80 ^° G. After this temperature had been maintained for 10 minutes, alkali was added in order to bring the pH to 9. 10 minutes later the sample was taken from it, with water and extracted x 30 minutes at 100 ⁰ G and then dried for 10 minutes at 110 g. the area shrinkage after 1 hour test in a washing machine (6,8 kg = 15 lbs) was 2%.

Example 24

Using the procedure given below, a thiol-containing polymer prepared: A mixture of 100 g (0.0995 mol) of a poly (tetramethylene oxide) diol with a molecular weight of about 1000 (Polymeg 1000), 19.9 g (0.133 mol) of 2-mercaptosuccinic acid (thio malic acid), 50 ml of toluene and 2 g of toluene-4-sulfonic acid monohydrate was refluxed under nitrogen and with stirring, the water of reaction and the water of hydration were removed by azeotropic distillation in a Dean-Stark apparatus. After 1 hour the precalculated was done

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26Π9206

Yolumen of water accumulated in the template and during the for the next 30 minutes nothing more distilled. The reaction mixture was cooled, further diluted with toluene, washed several times with water to remove the acid catalyst to remove and dried with anhydrous sodium sulfate. The solvent and other impurities with lower Molecular weights were then removed under reduced pressure to give a colorless, viscous polymer,

The resulting polymer with a terminal carboxyl, which on average contained 4 thiol groups per molecule, was then used in place of oligan in the procedure described in Example 23 and with the partially acid hydrolyzed Diisocyanate reacted to form a Product, the cationic amine groups and anionic carboxyl groups in the desired ratio and at least two remaining crosslinkable thio! groups per molecule contained.

This product was soluble in an alkaline solution and was applied to a fabric from an aqueous bath at a pH of 7 to 8 as indicated in Example 23 and then hardened (crosslinked). A shrink-proof finish was obtained.

Patent claims:

809838/0977

Claims (22)

Claims 1. Polymeric compound, characterized in that it contains at least one polymeric chain and cationic groups and at least two reactive groups per molecule, which can be crosslinked directly or by means of a crosslinking agent. 2. Polymeric compound according to claim 1, characterized in that it is both anionic and cationic
Contains groups. 3 · Polymeric compound according to claim 1 or “ _; 2, thereby
characterized in that it contains a polyether, a polyamide, a polyester or a polyurethane as the polymeric chain. 4-, polymeric compound according to any one of claims 1 to 3, characterized in that it is crosslinkable, cationic
Contains groups. 5. Polymeric compound according to one of claims 1 to 4-, characterized in that they are cionic groups as ka "
Contains protonated amino or acetidinium groups. 6. Polymeric compound according to any one of claims 1 to 4-, characterized in that they are cationic groups
Contains sulfonium, isothxuronium or pyridinium groups. 7 · Polymeric compound according to one of Claims 1 to 6, characterized in that it contains crosslinkable anionic groups contains. 8. A polymeric compound according to claim 7, characterized in that it contains thiosulfate or carbamoyl sulfonate groups as anionic groups contains. SG9838 / 0977 26U92Q6 9 · Polymeric compound according to one of claims 1 to 7? characterized in that it contains carboxyl or sulfonic acid groups as anionic groups. 10. Polymeric compound according to one of claims 1 to 9 » characterized in that they are isocyanate groups as crosslinkable groups contains. 11. Polymeric compound according to one of claims 1 to 9 » characterized in that it contains thiol groups as crosslinkable groups. 12. Polymeric compound according to claim 2, 5> or 11, characterized characterized in that it contains a polyether as the polymeric chain and carboxyl groups as the anionic groups. Process for the preparation of the polymeric compound according to one of Claims 1 to 12, characterized in that a prepolymer containing at least one polyether, polyester, Polyamide or polyurethane chain and contains a large number of reactive groups per molecule for introduction of anionic and / or cationic and / or crosslinkable Groups in the molecule can react to form a polymer Compound which contains cationic and preferably also anionic and at least two crosslinkable groups per molecule. 14-, method according to claim 13 for the production of a polymer Connection according to claim 5> characterized in that that a prepolymer with terminal isocyanate is reacted in organic solution with mineral acid. 15. The method according to claim 14, characterized in that the remaining isocyanate groups in the converted prepolymer are reacted with an alkali metal bisulfite. 809838/0977 26Π9206 16. The method according to claim 13 for producing a polymer Compound according to Claim 5 or 8, characterized in that a polyamide / epichlorohydrin resin is combined with a Reacts alkali metal thiosulfate. 17. The method according to claim 13 for producing a polymer Compound according to Claim 6, characterized in that a prepolymer with isocyanate at the end is used with a haloacetic acid and the product obtained is reacted with thiodiglycol, thiourea or pyridine. 18. The method according to ^: claim 13 for the preparation of a polymeric compound according to claim 9j, characterized in that a prepolymer with terminal isocyanate is reacted with a haloacetic acid and the product obtained is reacted with thioglycolic acid. 19 · Method according to claim 13 for the production of a polymer Connection according to claim 5i, characterized in that an isocyanate-terminated prepolymer is at least partially hydrolyzed to form terminal amino groups and the latter reacts with epichlorohydrin. 20. The method according to claim 13 for producing a polymeric compound according to claim 12, characterized in that that at least one thiol group of a prepolymer, which contains at least one polyether chain with thiol containing dxcarboxylic acid residues connected and / or by such residues are complete, can react for introduction cationic substituent group to form a compound having at least two crosslinkable groups per molecule. 21. A method for treating keratin fibers, characterized in that c.3.3 can apply a polymeric compound according to one of claims 1 to 12 from an aqueous bath (scoops) and harden the polymeric compound on the fibers. 609838/0977 26,9706 tet (networked). 22. wool, characterized in that it is the hardened (crosslinked) product of a polymeric compound according to a which contains claims 1 to 12. 609838/0977 _C0PY Blank page