DE2042989A1 - Treatment of materials containing keratin - Google Patents

Description

CIBA AKTIENG E SELL SCHAFT, BASEL (SWITZERLAND)

Case AHL Ij5 ^f 3 / E

Germany

Treatment of materials containing keratin.

The present invention relates to a method for modifying materials containing keratin, namely in particular a process to make the material resistant to shrinkage and to give the product permanent DUgelelgon-

109811/2069

to lend stocks.

A number of methods are already known for making keratin-containing materials shrink-proof, with some of them have a resin product applied to the fabric or fiber form. In the process of making the enema tight, the dimensions of the keratin-containing material are caused by felting Stabilized running-in.

Process to make caratinous materials permanent To impart ironing properties are also known. Many of them will be the same or similar Resins applied as they are used in the methods of shrinkage. In some procedures for Non-iron finishing is given to the keratin-containing material in the desired shape before the resin cures. On that the resin is allowed to harden while the material is in the desired shape, e.g. in the form of bow or pleated folds is held. In other methods, the resin is applied according to the material to be treated the desired Shape was given. The non-iron finish stabilizes the shape and surface softness of the material against deformations that can be caused by aqueous solutions. The desired shape can be the material before or after the treatment with the resin by methods well known to the person skilled in the art, which process the

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use of agents such as water, reducing agents and bases include.

It is desirable, but not essential, that the after methods of imparting dimensional stability and easy iron treated keratin-containing materials can be washed in household washing machines. Around To be washed in washing machines, the layer applied to the treated material requires vigorous agitation Can withstand warm or hot water containing detergent; these requirements require one tough test for the shrink-proof, wrinkle-proof and non-iron finishes.

It has now been found that certain esters with terminal mercapto (thiol) groups with success for shrinkage, Wrinkle-free and iron-free equipment can be used. These esters harden, i.e. react on the keratin fiber, the cure rate was found to be regulated by selection of an appropriate catalyst can be.

The method according to the invention for aftertreatment of keratin-containing materials is characterized in that one

(1) the keratin-containing material with a polythiol ester the formula

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O ("CO) R ₂ -SH

treated, wherein R is a preferably aliphatic hydrocarbon radical with at least 5 and at most 60 carbon atoms, R, an alkylene group with at least 2 and a maximum of 6 carbon atoms, Rp a hydrocarbon radical, a, χ and y in each of the p-chains each denote the number 0 or 1, where χ and y are different from one another, ρ is an integer of at least 5 and at most 6, q is 0 or a positive number of at most 3 and (p + q) at most 6 and (2) curing the polythioester on the material.

The present invention further encompasses keratin-containing materials which, if desired, are in the form of Piece goods are present and carry an above-mentioned polythiol on the surface, which is hardened or still hardenable is.

The treatment according to the invention for imparting dimensional stability and ease of ironing creates fibers or Piece goods that retain their original dimensions and shape when washed in machines. Thieves-

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Treated materials also have a high crease recovery , which is an important property for cloths that are used for the manufacture of trousers, since in trousers it is very easy to form gaps in the area of the knee or the hollow of the knee. Of course, crease resistance is also an important property of many other items of clothing.

In addition to preventing or delaying fungal shrinkage, prevent or delay those used in the process according to the invention Polythiols also reduce sagging, which is an important problem in knitted and woven textiles.

The term "koratinhaltige materials" used in the present description includes all forms of vox \ keratin fibers or textiles and garments made from them such as fleeces, slivers, card slivers, noils, yarns, weft yarns, staple fibers, non-woven fabrics, woven fabrics and knitwear. The method according to the invention can be applied to piece goods or finished items of clothing. Under certain circumstances, however, it may also be desirable to manufacture shrink-resistant fibers, for example in the form of tails. In fact, it is particularly expedient to treat materials containing keratin in the form of loose wool, slivers, slivers, card slivers and yarns, in the form of balls or yarn packages; in some cases the treatment leaves a slightly hard film

10 9 8 11/206 9

the paser, which, however, in the subsequent mechanical Treatment of the fiber, e.g. when weaving, is largely removed again. The material to be treated can be either made entirely from keratin fibers or from mixtures of these fibers with synthetic fibers such as those made of polyamides, Polyesters or polyacrylonitrile or with cellulose fibers including those made of regenerated cellulose. In general, however, the material used should contain at least 30 percent by weight of keratin fibers, with better results being obtained with materials that are $ 100 keratinous fibers.

The keratinous materials can be natural or recycled. Preferably, but not necessarily, they are made from sheep's wool. They can also be made from Alpaca, cashmere, mohair, vicuna, guanaco, camel hair, llama hair and mixtures of these materials with sheep's wool.

Those preferred for the treatment according to the invention Polythioesters conform to the formula

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OH

qy

[ε] - [cooh]

qx

^x (co) —o— (co) -

wherein p ^ q, χ, y and R have the meaning given above and FU have an alkylene group such as such a formula

C H "denotes in which ra is an integer from 1 to 9 or m 2m

even 12 stands; preferably represents R-, a -CHp-., or -CH ₂ -CHp- group.

A particularly preferred group of such polythiol esters is given by the formula

OH J '

O — CO— ^ R ^ —SH, 3 JP

and another preferred G group by the formula

1098 11/2 0

O- CO-R-SH

in which R, R. ,, ρ and q are those given above Have meanings and Rp- is an aliphatic hydrocarbon radical represents with at least 5 and at most 6 carbon atoms.

These polythioesters are generally known compounds and can easily be replaced by partial or complete Esterification of a * polyhydric alcohol (polyol) of the formula

with a mercaptocarboxylic acid H00C-R, -SH. The mercaptocarboxylic acid is preferably thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid or Mixtures thereof, although other mercapto acids such as mercaptoundecylic acid, Mercaptostearic acid and o-mercaptobenzoic acid can also be used.

Polyols that are suitable as starting materials are e.g. glycerine, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, Hexane-l, 2,5-triol, hexane-l, 2,6-triol, pentaerythritol, Dipentaerythritol, mannitol, sorbitol, polyvinyl alcohol, styrene

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_ 9 -

Allyl alcohol copolymers, partially hydrolyzed polyvinyl esters or acetals and hydroxyalkyl acrylate,
methacrylate and itaconate polymers and copolymers.

The polythiol esters of the formula IV in which q is 0 are very particularly preferred.

Another preferred group of polythiol esters
are those of the formula

^300H ] and

where R and ρ have the meanings given above and R ₁ . is an alkylene group, such as, for example, one of the formula C _n H ₂ , where η is an integer from 2 to 9 or even 12,
preferably -CH ₂ CH ₂ - or -CH ₂ CH (CH,) - and u is 0 or 1. Polythiol esters of the formula are also preferred

1 098 11/2069

-0-R.-SH

0OH

wherein R;,., ρ and u have the meanings given above and R / - is a hydrocarbon radical of 3 to 60 carbon atoms represents.

These polythioesters, too, are generally known products and can easily be prepared by partial or complete esterification of a polycarboxylic _{acid R (COOH) / _ + u} \ with a hydroxy mercaptan · HO-Rg-SH. Further preferred are those esters which are obtained by complete esterification, ie those of the formula

GOO-R.-SH

Polycarboxylic acids that can be used as starting materials here are, for example, citric acid, tricarallyl acid, mellitic acid, trimellitic acid, pyromellitic acid, tri-

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merized linoleic acid and polymers or copolymers of monoethylenically unsaturated acids and anhydrides such as acrylic acid, methacrylic acid and maleic acid.

According to the invention, the polythioesters can alone or in connection with aminoplasts, polymeric or not polymeric polymercaptans, epoxy resins (i.e. compounds that, on average, have more than one 1,2-epoxy group per molecule contain), acrylic resins, including polymers and copolymers of acrylic acid esters such as ethyl, n-butyl and 2-hydroxyethyl acrylates, as well as acrylamide or polyisocyanates, including prepolymers of e.g. a poly (oxyalkylene) glycol with an aromatic diisocyanate or a poly (oxyalkylene) triol with an aliphatic Diisoeyanate can be used.

Particularly preferred polymeric polymercaptans which

used according to the invention in conjunction with the polythiol esters are those esters or ethers that have at least two mercapto groups per molecule and

a) the rest of a polyhydric alcohol,

b) at least two poly (oxyalkylene) chains connected to this radical and

c) linked to carbon atoms via oxygen atoms in these poly (oxyalkylene) chains ν contain at least two residues which are either Murereste of an aliphatic mercaptoearboxylic acid or after removal of a hydroxyl group,

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2ÜA2989

Represent residues of allphatic hydroxy mercaptans,

these esters or ethers having a molecular weight of at least 400 and at most 10,000.

Examples of such esters or ethers correspond to the formulas

-) ^ - OH

-alkylene

(O-alkylerr) O — CO — R “—SH

(O-alkylene) OH

(-0-alkylene-) 0-CH ₀ CHOH ₀ SH

s d \ d.

OH

where R _{7 is} an aliphatic radical having at least 2 carbon atoms and each of the "alkylene" groups contains a chain of at least 2 and at most 6 carbon atoms, s is an integer which can have different values for each of the chains, ν is an integer of at least 2 and at most 6, t is 0 or a positive number such that (t + v) is at most 6 and R is the above

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has given meaning, the esters and ethers being preferred have a molecular weight of 1000 to 5000.

The esters and ethers mentioned above are commercially available.

Other polymeric polymercaptans that are to be used in connection with the polythiol esters according to the invention can be used are homopolymers and copoly- | merisate of butadiene or methylbutadiene, directly to Carbon atoms of the polymerization product bound Have mercapto groups. Such compounds correspond, for example, to the formula

HS-

-SH

in which b and d are each such an integer that the Polymer has an average molecular weight of at least 1000 and at most 10000, c 0 or an integer, X hydrogen or methyl and Y -CN, -COOH, -CONHg, -COOZ, -CgHf-, or - OCOZ i3t, where Z is an alkyl group with 1 bi3 is 8 carbon atoms.

Polybutadienes of this type containing terminal mercapto groups are also commercially available.

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20A2989

Non-polymeric polymer captans can also be used such as the bis (thioglycolates) and bis (3-mercaptopropionate) of ethylene glycol and propylene glycol are used.

Many of those in the process of the invention Polythiolesters used are insoluble in water, but can be in the form of aqueous dispersions or emulsions can be applied. Preferably, the polythiol esters are dissolved in the piece goods and garments organic solvents such as alcohols, lower ketones such as ethyl methyl ketone, benzene or halogenated, in particular halogenated and / or fluorinated hydrocarbons that contain no more than 5 carbon atoms, such as those used in dry cleaning Solvents carbon tetrachloride, trichlorethylene and perchlorethylene.

The amount of polythiol ester used depends on the desired effect. For most purposes, amounts in the range of 0.5 to 15 percent based on the weight of the material to be treated are preferred. In general, 1 to 10 percent by weight of the resin is necessary to stabilize knitwear. A high degree of shrink resistance, wrinkle resistance, crease resistance and dimensional stability can be achieved in woven fabrics with relatively small amounts, for example with 1 to 5 percent by weight.

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The feel of the treated material naturally depends on the amount of polythiol ester used. By simple Experiments can determine the minimum amount of polythioester necessary to achieve the desired effect in each case will. In addition, the structure of the tissue also has an influence on the amount of polythioester required.

The desired results can sometimes be found in \

fully only after the polythiol ester has hardened completely can be achieved on the material. At room temperature, this can take 5 to 10 days or even longer. However, the curing reaction can be carried out by using a catalyst be greatly accelerated. In general, it is advantageous to add the catalyst to the material to be treated add at the same time as the polythiolester; provided this However, the catalyst can also be used beforehand or can be added afterwards. The curing time can be regulated by choosing a suitable catalyst. the The curing time selected in each case depends on the specific application purpose of the method according to the invention. the Catalysts can be organic or inorganic bases, siccatives, oxidizing hardeners or through be free radical catalysts, such as azodiisobutyronitrile, peroxides and hydroperoxides or Mixtures thereof. Primary or secondary amines, especially lower alkanolamines such as mono-

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and diethanolamine and lower polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Propane-1,2-diamine, propane-1,3-diamine and hexamethylenediamine be. Water-soluble oxides and hydroxides such as sodium hydroxide or ammonia can be used as inorganic bases can be used. Examples of suitable siccatives are calcium, copper, iron, lead, cerium and cobalt naphthenates. Examples of usable peroxides and hydroperoxides are cumene hydroperoxide, tert-butyl hydroperoxide, dieumyl peroxide, Dioctanoyl peroxide, dilauryl peroxide, methylethyl · -. ketone peroxide, diisopropyl peroxydiocarbonate and chlorobenzoyl peroxide. Other types of catalyst are sulfur and sulphurous organic compounds in which the sulfur is not exclusively in the form of mercapto groups, such as mercaptobenzothiazoles or derivatives thereof, dithiocarbamates, thiurarasulphides, thioureas, disulphides, Alkylxanthogen disulphides or alkylxanthates.

According to the invention, the fibers and fabrics are preferably treated at a p "which is greater than ¹ J, for example 7.5 to 12; under acidic conditions, the polythiol esters have a tendency to harden more slowly.

The amount of catalyst used can vary within wide limits. In general, sets of 0.1 to 20, preferably 1 to 10, based on weight of the polythiol ester used, necessary, although also

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larger quantities can be used.

The hardening of the polythiol ester will continue accelerated by the use of elevated temperatures. If particularly rapid curing is required, temperatures in the range from 50 to 18 ° C can be used. A high level of humidity in the presence of catalysts also tends to accelerate the hardening process.

The polythiol esters and, if appropriate, the catalyst can be applied to the keratin-containing Material are applied. If, for example, tops or fabrics are to be treated, the products can be impregnated be let them wander through a bath or them immersed in it. fJind garments or parts of To treat items of clothing, it is beneficial to spray them with thorn polythiol ester. It is even cheaper the garments in a solution of polythiolesters |

to overturn. For this purpose, those for dry cleaning are particularly useful machines used.

Should a shrink-proof finish be carried out werdon, os is generally better, the polythiol ester to apply to the keraline-containing piece goods, although it also, as indicated above, on the fibers in the form can be applied by combs or cardi-abanders. The fabric can be vr »r or · after the · Huharidlurig with the poly-

■ '. 1 o ⁽ yes a 11/2 ο 6 9

- l8 -

thiolester are smoothed ("flat-setting"). In this way the tissue will not only return to its original dimensions it also maintains its smooth, soft appearance during wear and after washing. It however, it should be noted that smoothing is not necessary and, for some types of fabrics, not even desirable. The smoothing or spreading is generally carried out in such a way that the fiber material is either steamed with excess pressure or treated with steam at atmospheric pressure in the presence of a smoothing agent and moisture the fiber material is held flat. Smoothing can also be achieved by having high concentrations a reducing agent and a swelling agent are applied, wherein the substance during washing off the excess funds are kept flat. Another method involves hardening in the smoothed state achieves that the keratin-containing product with a swelling agent and an alkanolamine carbonate, e.g. urea or Diethanolamine carbonate, the material is then dried and semi-decated. If desired, the fabric can also be smoothed with the polythioester, whereby the smoothing ("setting") and the shrink-proof finish carried out at the same time.

Should the keratin-containing material in non-iron equipment be subjugated, this can be done in different ways

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Because of being reached. One method is to mix the keratin-containing material with the polythioester The material is then treated into clothing or f ^ ile of it is processed and pleated or ironed folds incorporated using reducing agents, * superheated steam. The poly can also here at any time during the

the piece goods are applied to the fiber, "<ü, h% Φλ £ the fibers themselves, on the yarn or on the woven" If desired, agents that block the mercapto groups such as formaldehyde or higher alcohol can be applied to the With creases or pleats, garments can be turned over after the polythiol ester has hardened.

A preferred method of using the polythdol ester to achieve a permanent ironing effect in that a finished garment made from keratin Fiber or part of it that is already the desired Has pleats or creases with the in one organic! solvent-dissolved polythioester treated will. It is essential that the tolythiol ester in an organic solvent is used because the Treatment with aqueous systems only the one already presented Would make pleated or creases disappear again.

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Another method, which is mainly the production of permanent iron or pleated folds !! regards, the keratin-containing fabric is impregnated with the Polythiolester, then lays the bow or pleated fold and keeps the fabric in the folded state while Heat and pressure are applied.

In another method of smoothing ("flatsetting ^11" ) and making keratin-containing tissue firm in shape, the tissue is treated with a Gllttungsralttel ("setting agent * f, the held flat, still wet tissue glides through heating, ifflprEgiiiert it then with a vain aqueous Itaralsicm or dispersion the polythiol ester and- Catalyst * dries and heats it up and hardens the bolythlol ester. Finally, it is used to process the pleated or ironed folds, if desired, by steaming in the presence of a setting agent (* setting agent ¹ *) such as monoethanolamine sesquisialfit can be attached ..

Smoothing (* -setting ") of the piece goods keratinhaltigeti both before and after treatment with the polythiol ester of conventional methods is caused by the application For example, ^1I-setting agents." Are used as reducing agents, bases, water and superheated steam. Monoethanolamine sesquisulfite is the most common and can be used in

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binding with a swelling agent such as urea.

Those used in the process according to the invention Products can contain dirt repellants, antistatic agents, Contains bacteriostatics, anti-rotting agents, flame retardants or wetting agents. You can also what- water-repellent substances such as paraffin wax or polyethylene

emulsions and optical brighteners contain .. ^

The present invention now continues explained by the following exemplary embodiments. Unless otherwise stated, parts and percentages are given based on weight.

The treated cloth samples are washed at 4 "0Cl hour in an" English Electric Reversomatic "washing machine in an aqueous solution containing 2 g of soap flakes and 0.8 g of anhydrous sodium carbonate per liter, a plot ratio of about 1:30 being used The cloth samples are then washed with cold water, wrung out in the machine and then dried for 30 minutes in a Parnall Tumble Drier at full heat. Shrinkage is measured as the difference in the dimensions of the fabric before and after washing Surface shrinkage is calculated from the measured linear shrinkage.

The polythioesters used are as follows

1 Ü ö 8 1 ^{1/2063 ßAD OR} '® * NAL

made: A mixture of 184 g glycerine, 552 g thioglycolic acid, 4 g of p-toluenesulfonic acid and 500 ml of perchlorethylene are refluxed under a nitrogen atmosphere in such a way that this occurs during the reaction formed water is drawn off. After 5 hours, 104 ml of water have been collected (calculated amount 108 ml). When cooling the product partially separates from the perchlorethylene. The solvent is separated off and the product with Water washed and dried. There are 600 g of practically pure glycerol tris (thioglycolate), a clear liquid with a mercapto group content of 8.88 equivalents per kg (theoretical value: 8.93 equivalents / kg).

In a similar way, the following products are made: 1, l, l-trimethylolpropane-tris- (thioglycolate) (Mercapto group content 7 * ^ 5 equivalents / kg, theoretically: 8.43); 1,1,1-trimethylolethane tri- (thioglycolate) (mercapto group content 8.50 Equivalents / kg, theoretical: 8.78); Hexane-1,2,6-triol-tris (thioglycolate) mercapto group content 7.72 equivalents / kg, theoretical: 8.40); Dipentaerythritol tetrakis (thloglycolate) (Mercapto group content 7 * 30 equivalents / kg, theoretical: 7 * 27); Glycerine tris (2-mercaptopropionate) (Mercapto group content 7.58 equivalents / kg,. theoretically 8.43) and the thioglycolate of a styrene-allyl alcohol copolymer. The SfcyroX allyl alcohol copoly-

1Q t) e -11 / 2 ü 0: ^% ■ "

20429S9

The styrene-allyl alcohol copolymer has a molecular weight of 160D and contains 5 * 35 hydroxyl groups per molecule. The! Has a mercapto group content of 2 ^, 15 equivalents- ^ «Lh. about 8o $> des I ¹ Ur ein Pentakis- (thioglycolate) Mertes * Pentaeryfchrit-tetrakiiS-Cthioglyeolat) ^ O-mereapto-propionat) _a Oipenta-

rand Bipentaeir'jrtlirit-hexakis- *

are in trade: «rtoiltlinh»

Semisch of 100 g of 10% 3 Etepol _Ä {2.beta ml = 29.5 ®1 1 g p-ToluDl-suiironslure rniä ISO »1

16 hours under a SZldks% oTt ~ such; at the Hüek river zma. Boiling -heated ^ »that

formed TSasser 0.6 aalJ removed will * Me liSsaang. wi ^ d washed with water and the solution

^ wöätareH 111 g of a pale gelatinous oily

Liquid with a mercapto group content of 2 ^, 20 Äe <p.ivalenteÄ / k; see ^ theoretical amount about 2> 8 equivalents / kigl

Others know about Ferehleräthylen Solvents such as toluene are used *

¹¹ SHpOL 10% 3 ^1t is a trimerized unsaturated fatty acid with 18 carbon atoms and a molecular weight of about 800 and a carboxy group content of 3.42 equivalents / kg. It is from Unilever-Emery NV,

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. 24_ 2042983

Gouda, Holland.

In one example, a palythiol ester according to the invention is dispersed in an aqueous phase, a Emulsifier (such as an adduct of a long-chain primary aliphatic amine and ethylene oxide) and optionally a protective colloid (such as sodium arboxymethyl cellulose or the sodium salt of a methyl vinyl ether-maleic anhydride copolymer) are particularly suitable for the treatment of keratinous material.

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example 1

The cloth used is a wool flannel with

a weight of 170 g per square meter; the p "value

its aqueous extract is 3 * 1 · The Planeil is in a 3 $ solution of the polythiol ester in triehloroethylene, which, based on the weight of the poly "

thiolesters, $ 10 monoethanolamine contains 8% polythioester and accordingly Ο, δ ^ ί. Monoethanolamine padded. In order to completely dissolve the monoethanolamine, the solution also contains 5% ethanol. After the treatment, the flannel is dried in a fan oven at 50 ° C. and then stored at room temperature with the admission of air. The samples are washed and then examined for shrinkage. A sample of the planel cloth is subjected to the sharp wash without pretreatment with a polythiolester. Table I shows the results obtained.

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Table I.

Loss of area (%) after washing
after hardening during (days) 2 4th 8th untreated 1 20.5 22.6 21.3 treated with: 20.0 Glycerin-tris- (thio-
glycolate) ii, 3 10.3 1,1,1-trimethylolethane
tris (thioglycolate) 8.5 8.0 ^; .; 5 ^ o; ;; ■ ".. 1,1,1-trimethylolpropane
trls- (thioglycolate) 8.9 14.3 9 * 4 Hexane-1,2,6-triol-tris-
(thloglycolate) 11.5 9.4 Tris- (2-mercaptoethyl) -
ester of "Empol 1043" 12.2 14.5

Example 2

The study described in Doispiel 1 ι ^v repeated using other polythioester. The wool-tannel used is similar to that of Example 1, xdfc-rr. However, the p "value of its aqueous extract is 7.0. Ethanol is only added to the trichlorethylene solution when using monoethanolamine as a catalyst.

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Table II Loss of area {%) after (days)

untreated

treated with:

Pentaerythritol tetrakis (thioglycolate)

Dipentaerythritol-tetralc; is- (thioglycolate)

Dipentaerythritol hexakis (thioglycolate) Dipentaerythritol - * exakis- (3-mercaptopropionate) .

Castor oil tris (thioglycolate), styrene allyl alcohol poly (thioglycolate)

Glycerine tris (thioglycolate) (1,2) glycerine tris (2-mercaptopropionate)

(1.2)

Glycerine tris (thioglycolate) (1, *) Pentaerythritol tetrakis (thioglycolate)

Pentaerythritol tetrakis (thioglycolate)

Pentaerythritol tetrakis (thioglycolate)

1,1,1-trimethyiolpropane-tris- (thio-

glycolate) (6)

1,1,1-trimethylolpropane tris (thioglycolate) (?)

Mannitol hexakis (thioglycolate) (1.2) 22.5

7.7

10.0

17.3

15.9
16.8

19.2
18.6

22.2

11.3

15.0

16.8

I. 14.5

18.6

22.2

9.3 8.7

13.1 7.4

12.7 10.7

10.7 14.6

12.6 9.4

7.9 6.4 5.0

15.51

(1) Polythiol absorption 3 %

(2) Monoethanolamine intake 0.3 %

(3) catalyst 1.2 % calcium naphthenate (containing 5 # Ca)

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(4) Catalyst: 0.3 % tetramethylthiuram disulfite

(5) Catalyst: 0.12 % diethylenetriamine

(6) Catalyst: 0.8 % diisopropylxanthogen disulfite

(7) Catalyst: 0.8 % tetrabutylthiuram disulfite.

Example 3

This example explains the use of a polymer captan according to the present invention with another polymer captan or with an epoxy resin. It will be like la Proceed as described in Example 2. The results obtained are given in Table III.

"Thial A * means the bis (thioglycolate) one Poly (propylene glycol) with an average molecular weight of 2000.

"Tniol B" means the product "Hyear MISN * from the American company BF Goodrich Chemical Co. According to the manufacturer, the product has an average molecular weight of about 170 and is a polymerizate containing terminal mercapto groups and consisting of about 21 butadiene units and 7 acrylonitrile units per molecule. Es has structures that can be represented by the following formula:

1 Ü Ü 8 Ί ι /? ■■■ 3 9

HS-

2'3

SH

CN 7

"Epoxy resin A" is a polyglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane with a 1,2-epoxy content of 2 to 5ί2 equivalent / kg.

Table III

Ester % implemented with % catalyst % Loss of area (4)
after days 1 2 ■ 8 6th 2 0.8 14.0 11.2 8.8 Glycerin-tris- (thio-
glycolate) 6th Ethylene-glycol-bis-
(thioglycolate), 2 Monoethanol
amine 0.8 12.6 10.8 Glycerin-tris- (thio
glycolate) 6th Thiol A ν " 2 Monoethanol
amine 0.16 13.1 12.2 Pentaerythritol tetra
kis (thioglycolate) 2 Ethylene glycol
bis- (3-merkaptο-
propionate) 1 Diethylene
triamine - 14.0 ιο, 3 Pentaerythritol tetra-
kis- (thioglycolate 2 Thiol B. 1 - - 9.3 9.3 6.9 Pentaerythritol tetra
kis- ( thioglycolate) ⁺ ) 1.5 Thiol B 1.5 - 0.06 9.8 9.8 Pentaerythritol tetra
kis (thioglycolate) Epoxy resin A Diethylene
triamine

The treated samples are heated to 150 ° C. for five minutes before storage hardened.

CD OO CD

Example 4

Wollunte is up to an absorption of with a solution of!,!, L-trimethylolpropane-tris-thioglycolate) and Monoäthanolamiη padded in perchlorethylene, 3o that $ 8 polythioester and $ 0.8 monoethanolamine be included. The cheesed wool is then

ο ·

Dried for 30 minutes at 70 * C, after which they are taken under

Leaves air ingress. The effectiveness of the treatment is determined by measuring the shrinkage that occurs when the samples are washed (in cotton bags) using customary methods. Uri-treated samples of the combed wool show an 11-

linear shrinkage of 28.0 and 28.3 #, treated samples of 15.0 and 11.5 #, respectively.

10 981 ι /? '> 69

2042980

52 -

Example 5

An aqueous, pentaerythritol tetrakis (thioglycolate) containing aqueous solution is prepared as follows:

1 g of sodium carboxymethyl cellulose is used at 70 dissolved in water up to 80 C. After cooling, the solution becomes 100 g of the polythiol ester and 10 g of an anionic one Emulsifier (an adduct of 1 mole of a mixture of primary 16 to 18 carbon atoms n-Alkylamines with 70 mol of ethylene oxide are added. The entire Mixture is stirred with a high speed stirrer for 5 minutes.

12 g of this emulsion are diluted with 276 g of water. For this purpose, 12 g of a liquid aqueous solution are used of diethylenetriamine added as a catalyst. As described in Example 2, the wool flannel is made with this Emulsion padded. The thiol is then allowed to harden. The uptake of thiol is $ 2, that of diethylenetriamine 0.04 #. The wool flannel shows only 9 * 8 $ after washing after curing for one day at room temperature Running in.

In a second experiment, an emulsion as described above is prepared, but with the

1 0 9 S) '1 ' j 9

_ ₅₃ 2Ü42989

Tetrathiol is replaced by an equal amount of "Thiol B".

4 g of the "Thiol B" emulsion are mixed with 12 g the emulsion of pentaerythritol tetrakis (thioglycolate), 12 g of an aqueous solution of diethyl triamine and 272 g of water mixed. V / olle is padded as described in the example above. The cloth will be a day at Hardened at room temperature and then washed. Loss of area is only $ 8.3

10 9 8 11/2069

Claims (11)

Claims where R is a preferably aliphatic or araliphatic hydrocarbon radical with at least 3 and at most 60 carbon atoms, R, an alkylene group with at least 2 and at most 6 carbon atoms, Rp a hydrocarbon radical, a, χ and y in each of the p chains each have the number 0 or 1, where χ and y are not equal, ρ an integer of at least 3 and at most 6, q 0 or a positive integer of at most 3 and (p + q) at most 6 int and 2) hardens the polythiolester on the material. 2. The method according to claim 1, characterized in that that the polythiol ester of the formula 109811/2 0 69 2UA2989 j 0-CiO-It ₅ -SH j corresponds, in which R, an'alkylene group, in particular one of the formula -CH ₂ -, -CH (CH,) - or -CH ₂ CH ₂ and R, ρ and q have the same meaning as in claim 1. 3. The method according to claim 2, characterized in that the polythiol ester of the formula O-CO-iL-SH corresponds, wherein R ₁ - ^u stands for an aliphatic hydrocarbon radical having at least 3 R.- nd most 6 carbon atoms, the same meaning as in claim 2 and q and ρ have the same meaning as in the claim. 1 4. The method according to claim 1, characterized in that the polythiol ester of the formula 1 0 9 8 'M / 2! J b ¹ J .CO-OR ₄ -bra} COOH - ¹ U where R has the same meaning as in claim, Ru is an alkylene group, in particular of the formula -CHpCHp- or -CHpCH (CH,) -, ρ has the same meaning as in formula (I) and u is 0 or 1. 5. The method according to claims 1 to 4, characterized in that the polythiol ester in an amount of 0.5 to 15 $, based on the weight of the to be treated
keratinous material is used. 6. The method according to claims 1 to 5 * thereby characterized in that a catalyst is additionally used to harden the polythiol ester. 7. The method according to claims 1 to 6, characterized in that keratin fibers with the polythiol ester
can be treated with a p "value of 7 * 5 to 12. 8. The method according to claims 1 to 7, characterized in that the treated keratin-containing material to harden the polythiol ester to a temperature of 30 is heated to 180 ° C. 10 9 8 1 1/2069 9. Process for the shrink-proof finishing of keratin-containing Materials, in particular wool in the form of loose wool, carder ribbons, slivers, slivers or yarns in skeins or yarn packages, characterized in that a polythioester according to claims 1 to 4 is used the material applies. 10. Process for the non-iron finishing of keratin-containing materials, in particular woven or knitted materials ter wool, characterized in that a polythiol ester according to claims 1 to 4 is applied to the material applies. 11. An emulsion for carrying out the method according to claims 1 to 10, characterized in that that they a) a polythiol ester dispersed in the aqueous phase according to claims 1 to 4, b) an emulsifier and optionally 0) a protective colloid contains. 10981 1/2069