DE2429062A1 - METHOD OF MODIFYING A KERATIN MATERIAL - Google Patents

Description

I.V.S. NOMINEE COHPArTY LIMITED, London (England)

and
CIBA-GSIGY AG, Basel (Switzerland)

Cas e 1-8640 / + Germany

Method for modifying a keratin material

"The invention relates to a method for modifying keratin-containing fibers or keratin fibers; she "concerns in particular a method of shrink-proofing Keratin textile materialJen as well as a method with which Help such materials iron-free or true-to-shape dish can be.

The dimensions of the material against shrinkage due to felting or relaxation stabilized. The shape and surface smoothness of the material are created using the ironing process stabilized against deformation in the presence of aqueous solutions.

A method sum Modification of keratin-containing material or keratin material known, which consists in that the material with 0.5 to 15 wt .- #, based on the material, one Polythiol resin in the form of a solution in an organic Medium or treated in the form of an aqueous emulsion, • 4098 8 5/137 7

that has 3 to 6 thiol groups per molecule and a molecular weight has and contains between 4-GO and 10 CCO (a) a residue of a polyhydroxy alcohol, ("b) at least two poly (oxyalkylene) bound to this radical

Chains,
(c) 3 to 6 radicals from the group of an acyl radical of a thiol-containing aliphatic carboxylic acid and a radical (after removal of a hydroxyl group) of a thiol-containing aliphatic alcohol, bonded via oxygen atoms to carbon atoms in these poly (oxyalkylene) chains,

and curing the resin on the material. This PoIythiole may be used iron to the treated material and shrink resistant to make ₇ without thereby the grip of the material is impaired.

A further development in this area is described in German Offenlegungsschrift No. 2 162 066, which describes a method indicates to modify keratin material, in which this is treated with a polythiol as indicated above and an aliphatic polyamine-epichlorohydrin resin.

It has now been found that the resistance to shrinkage (the shrinkage resistance) and the permanent ironing properties (the freedom from ironing) of the modified keratin material thereby Can be further improved by using stabilizers against the disadvantageous at the same time as the resins mentioned above Influences of light on the keratin materials. The effect of the polythiols can be improved in an unexpected manner, resulting in permanent, light-resistant surface coatings (Finishes) leads.

The invention relates to a method of modification of keratin-containing material or keratin material (hereinafter always referred to as keratin material), which is thereby identified

409885/1377

is drawn; that the material is treated with an organic solution or an "- aqueous emulsion" which contains

1.) 0.5 Ms 5 wt .- ^, "based on the weight of the keratin material, of polythiols with at least two thiol groups per LIoI ekül and a molecular weight between 400 and 20 OCO, which are reaction products of a) -. ' Po Iy alkoho 1 e η,

b) alkylene oxides and / or dicarboxylic acids, carboxylic acids containing C ^) thiol groups or Cp) epihalohydrins and alkali hydrogen sulfides (these polythiols contain ether and / or ester bonds). or from '■■ "■"
a ^) polycarboxylic acids,

"b ^ j) Alkylenoxydeη or dialcohols.und c ^) represent carboxylic acids containing thiol groups,

2. ) 0.1 "to 0.2% by weight, based on the weight of the keratin material, of monomeric stabilizers against the adverse effects of light, and

3.) optionally 0.1 to Λ wt .-%, based on the weight

of the keratin material, to condensation products of • d) Bicyandiainid, Cyananid or another bifunctional Compound or a mixture of two or three of these components,

e) a polyaniine with at least three piria and / or secondary amino groups and

f) 'of an epihalogenhydrin,

and that the treated material is dried and optionally hardens. ''

The polythiols with at least two thiol groups per molecule And a molecular weight of 400 to 20,000, preferably from 4OC to 10 000, contain '-

40988 5/1377 ■:

"2 ^ 29062

a) a residue of a polyhydroxy alcohol

b) at least two poly (oxyalkylene) chains bound to this radical or diacyl radicals and, in the form of an ether- or ester-like bond,

c) at least two via oxygen atoms to carbon atoms radicals bonded in these poly (oxyalkylene) chains and diacyl radicals from the group of an acyl radical of a thiol containing aliphatic carboxylic acid or a residue (after removal of a hydroxy group) of a thiol containing aliphatic alcohol or

a ^) the acyl radical of a polycarboxylic acid, b ^) at least two oxyalkylene radicals bound to this acyl radical and

c ^ j) containing at least two acyl radicals of thiol groups Acids. '

The polythiols usually contain up to six thiol groups per average molecule and will produce particularly good results obtained with polythiols containing three or four thiol groups per average molecule.

Suitable polyhydroxy alcohols include ethylene glycol, poly (oxyethylene) glycols, propylene glycol, poly (oxypropylene) glycols, Propane-1,3-diol, PolyCepichlorhyrlrinCe)), Butane-1,2-diol, Butane-1,3-diol, butane-1,4-diol, butane-2,3-diol, Poly (oxy-1,1-dimethylethylene) glycols, PolyCtetrahydrofuranCe)), Glycerine, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, Hexane-1,2,5-triol, hexane-1,2,6-triol, pentaerythritol, dipentaerythritol, Mannitol, sorbitol and adducts of alkylene oxides with ammonia or amines, such as diethanolamine and tetrakis (2-bydroxyethyl) ethylenediamine.

Suitable alkylene oxides include ethylene oxide, propylene oxide and, less preferred, the butylene oxides, epichlorohydrin or tetrahydrofuran. If desired, the polyhydroxy alcohol with an alkylene oxide, e.g. propylene oxide,

409885/1377

2A29062

treated and then provided with an end group of another Alkyienoxyds, such as "for example Äthylenoxyd _v (closed).

Preferred mercaptocarboxylic acids for the esterification are thioglycolic acid (2-Iiercaptoessigsäuro) and 2- and 3- ^ ercaptopropionsiiure, to other mercaptomonocarboxylic acids, which also Can be used include hsrcaptoundecylic acid and mercaptostearic acid.

Preferred polythiols are those of the general formula

(D [R)

) 0 (CO), X]

• π W-I ρ

where mean:

m is at least 1, where m is in each of the -O-alkylene chains can have the same or different fourths,

w 1 or 2, ρ at least 2, (p + Q.) an integer from 3 "to 7?

each alkylene group being a chain having at least two and at most six carbon atoms between successive ones

Contains oxygen atoms,

E is an aliphatic one containing at least two carbon atoms Rest and

X has at least one thiol group and 1 to 18 carbon atoms containing aliphatic radical.

The oxyalkylene units in the individual poly (oxyalkylene) chains can be different. You can if you want be substituted for example by phenyl or chloromethyl groups.

It can therefore be the partially or fully esterified Compounds of the general formula can be used

, 409885/1377

L (O-Xlkylen O

(2) fR 1 ¹

where "mean:

R ^ is an aliphatic carbon residue with 2 to 6

Carbon atoms,

each alkylene group having a chain of at least two
and contains a maximum of six carbon atoms between successive oxygen atoms,
m at least 1, where m in each of the -0-alkylene chains denotes

can have the same or different values, P ^ an integer from 2 to 6, (P-i + Q.) An integer from 3 to 7 and u 1 or 2.

Esters of the general formula are particularly preferred

[R ₂ 3. [(O-alkylene OjD «CO

v / orin mean:

Eo is an aliphatic carbon residue with 3 "to 6

Carbon atoms,

each alkylene group having a chain of at least two
and contains a maximum of six carbon atoms between successive oxygen atoms,
m at least 1,

Po is an integer from 3 "to 6 and u Λ or 2.

The esters according to formula (3) are esters
based on glycerine, hexane-1,2,5-triol or hexane-1,2,6-triol and ethylene oxide and / or propylene oxide, ie those of the general formulas

409885/1377

CH

and

CiI -

CH- CH

--H

^{O 'CO' C} u ^H 2u ^SH

where m and u have the meanings given above and t 2 or 3 means. .

The most for the purposes of the present invention preferred polythiol esters are those made from glycerine, propylene oxide and thioglycolic acid, i. those of the general formula

CH ₂ - (OC ₃ H ₆ ) _m OC OCH ₂ SH

CH -

CH ₂ - (OC ₃ H ₆ ) _m OCOCH ₂ SH

OCOCH ₉ SH

\? orin m has the meaning given above, with a molecular weight within the range of 1000 to 6000. Such esters are commercially available.

409885/137 7

These thiol-terminated poly (alkylenox, 7d) esters can easily be prepared by reacting a polyhydroxy alcohol with an alkylene oxide and then reacting "Esterification of the terminal hydroxyl groups with a mercaptocar" acid. ■

The second class of terminal alkylene oxides Thiol groups include ethers of the general formula

[(O-alkylene) _mq1

[(O-alkylene) ^ H ₂ CHCH ₂ SH]

R ₃

where "mean:

R is an aliphatic radical with at least two carbon atoms,

wherein each alkylene group is a chain with at least zv; ei and contains a maximum of six carbon atoms between successive oxygen atoms,

R ₃ , a radical from the group -OH, - (O-alkylene) -OH, _0-C0-C _u H _2ü -SH and - (O-alkylene ^ -O-CO-C ^^ - SH, where ν is an integer of at least 1 and u is 1 or 2,
m at least 1, where m in Q'eder der -0-Alky lenket th

ρ can have the same or different values and (p + q) can have at least 2 and an integer from 3 to 7.

The oxyalkylene units in the individual poly (oxyalkylene) chains can also be different, they are, however, preferably the same and they can, if desired, for example be substituted by phenyl or chloromethyl groups. -

409885/13 77

Preferred among such ethers are those of the general Formulas

(8th)

and

(9)

(OC _t H

Ah

(OC. H ₀ ,.) OCH ₀ CHCH ₀ SH t 2trm .2 | 2

OC

OCH ₂ SH

where "mean:

Ro is an aliphatic hydrocarbon radical with at least 3 and at most 6 carbon atoms,

m at least 1,

an integer from 3 to 6 and 2 or 3. '

As special representatives of the compounds of the formulas (8) and (9) are the compounds of the following formulas:

OH

(10)

OH

CH - (OC ^ H _r ) OCH ₉ CHCH ₀ SH

OH

CH ₂ - (OC ₃ H ₆ ) _m OCH ₂ CHCH ₂ SH

where m is a positive integer having a molecular weight within the range of 700 to 6000, and

409885/1377

- ΊΟ -

- (OC ₃ H ₆ ) _m OCH ₂ CHCH ₂ SH

OCOCH ₂ SH

CH - (OC ₃ H ₆ ) _m OCH ₂ CHCH ₂ SH (11) OCOCH ₂ SH

OCOCH ₂ SH

wherein m is a positive integer, having a molecular weight within the range of 700 to 6,000.

The ethers of the formula (7) _} in which R 1 denotes -OH can be prepared in a manner known per se by reacting an alkylene oxide with a polyhydroxy alcohol, etherifying the hydroxyl groups of the product with epichlorohydrin and treating with sodium hydrogen sulfite to replace the chlorine with a sulfhydryl group can be produced (see US Pat
5 258 4-95 and British patents 1 76 725 and
Λ 144 761). In many cases, the average number of thiol groups per molecule is not an integer, but can
be for example 2.6. This is partly due to the fact that the chlorine atom is not completely replaced by the -SH group, and partly to level reactions: for example, the chlorohydrin ether obtained by reaction with epichlorohydrin can also react with epichlorohydrin to form an ether that originally contains two replaceable chlorine atoms present in the polyhydroxy alcohol
Contains hydroxyl group

Ethers of the formula (7), in which R, - (O-alkylene ^ OE means can be prepared by treating the epichlorohydrin, the alkylene oxide and the polyhydroxy alcohol produced Product first with an alkylene oxide and then with sodium hydrogen sulfide (sodium hydrosulfide) (cf. the British Patent specification 1,144,761).

, k 0 9 8 8 5/1 3 7 7

The iitheresters of formula (7) in which R _{7 is} —O-CO-C EL SH or - (O-alkylene) _v O-GO-C _u H _2u SH - are obtained by esterification of the corresponding alcohol with a mercapt © carboxylic acid HOOCGpHp SH.

The second major class of "preferred polythiols include Polyester of the general average formula

(o) _r co (o) _q z (o) _q co (o) _r YSH j

_r co (o) _q z (o) _q

where "means:..

q and r, which are not the same, 0 or 1, ρ is a positive integer of at most 6, Z is a divalent organic radical that has an or : several 'of its carbon atoms to the specified

-Ο- or -CO units are bonded, Y is a divalent organic radical that has an or several of its carbon atoms, to the indicated i-SH group and the indicated -0- or -CO units

is bound, and
W is an organic radical which must contain at least one -SH group, if ρ. = 1, which via one or more of its carbon atoms to the specified -0- or

■ -CO units is bound.

The average structures of the preferred esters can in particular are represented by one of the following general formulas:,

409 885/137 7

(13)

(14) (15) (16)

(17) (18) (19) (20)

13th

-

O-CO-R -CO-O-R SH

13th

CO-OR ¹² O-CO-R ¹⁶ SH

R-. 0-- CO-R-CO-O-R

1 16 1

-0 CO-R SH

Χ Col OR ¹² -Q-CO-R ¹¹ CO -LO-R ¹⁵ SH J

, 11

, 12

^ S \ S \ / \ ΎΊ ** Ψ

CO-R-CO-ORO -CO-R COO-R SH 11 * 1 19 1 fi

J-K "U" UrK - <JJ -U U ^ K. UoU-Λ Ott

it

Λ2,

O-CO-R -CO -4- OR OH
s

H - [0- _R ¹² -

HSR ¹⁶ -C0-0-R ¹² -0-L COR ¹⁴ COOR ¹² O J- <

L -J _t

COR ¹⁶ SH

"and in particular by one of the following general formulas

(22) (23) (24) (25) (26)

13 R ..

11

CO-R -CO-O-R

t OCO-R ¹ ^ "- CO-OC H. SH m 2m

R ¹³ ._ CO-OR ¹² HD-CO-CH ₂ . SH -0 -L CO-CI

CO-R ¹¹ COOC H. SHΊ rn 2ra J

0-R ¹² -0-C0-R ^{1: L} -C0 1 OC H- SH Ί

r - Ί

^ k C0-0-R ¹² -0-C0-R ^{1: L} -C0 lo-R ¹² -O-CO-CH ₂ .SH

LL J _t J ₈

, 13

, 13Γ

"IL o J. cc-R ⁿ -co-cR ¹² -o

(27) H.

0-R ^12-0 -C0-CH_CHCO

² I.

SH OR ¹² OH

HS-CH _0. -CO-0-R ^12-0

j 2 j CO-CH CHCO-OR ¹² Ο

409885/137 CO-CH ₂ -SH

where mean:

j is 1 or 2 and m is 2 or 3,

11
R is the residue of an aliphatic, cycloaliphatic or aromatic carboxylic acid remaining after the removal of the "two -COOH groups,

R den after the removal of the two hydroxyl groups remaining residue of an aliphatic, araliphatic

or cycloaliphatic diol,

R is an organic radical containing at least two Kiohlenstof fatome contains and via its carbon atoms directly to the specified ester chains with terminal mer-

catrban is bound,

R the remaining after the removal of the -COOH groups

Remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid containing a mercaptan group,
t is an integer of at least 1,

s is an integer of at least 2,

R ^ SH den after the removal of an alcoholic hydroxyl group remaining remainder of a monomercaptan mono-

hydroxy alcohol and

R SH those remaining after removal of a carboxyl group Remainder of a monomercaptan monocarboxylic acid.

R means wise before ziags

(a) a saturated aliphatic carbon group with 2 to 10 carbon atoms that an -SH group can carry,

(b) a cycloaliphatic-aliphatic hydrocarbon group with 5 to 3 '+ carbon atoms, which is an ethylenic unsaturated

may contain, or

(c) a mononuelear arylene hydrocarbon group with 6 up to 12 carbon atoms.

R can be a saturated aliphatic hydrocarbon chain with 2 to 250 carbon atoms denote by methyl groups and substituted by -SH groups and by A'ther-

- 409885/137 7

oxygen atoms and interrupted by carbonyloxy groups can be.

E ^, if it is bound directly to an -O-I unit, can a saturated aliphatic hydrocarbon chain with 2 to 25O carbon atoms represented by methyl groups and substituted by -SH groups and by ether oxygen atoms and can be interrupted by carbonyloxy groups, and when it is bonded directly to a -CO unit, can it mean

(a) a saturated aliphatic carbon group with 2 to 10 carbon atoms, which can carry an -SH group,

(b) a cycloaliphatic-aüphatic hydrocarbon group with 5 to 5Ί carbon atoms that have an ethylenic unsaturation may contain, or

(c) a mononuclear arylene hydrocarbon group of 6 to 12 carbon atoms.

It should be noted that formulas 24-39 the Represent the average structure of the esters. Because of the incomplete esterification, other substances can also be used to be available. Here polyesters can be made by can be implemented together in any desired order

(a) a Monomercaptanmonocarbonsäure or a Monomercaptanmonohydroxyalkoho1,

(b) a connection with two, but no more than two, alcoholic hydroxyl groups and

(c) a compound containing at least three carboxylic acid groups .

If desired, components (b) and (c) can be mixed with one another be reacted to form an ester with a terminal hydroxyl or carbonyl, which is then esterified with (a) will. These esters can also be those that can be produced by esterification

409885/137 7

(d) a Konomercaptanedicarboxylic acid with

(e) one at least two but not more than six, alcoholic hydroxyl-containing compound and possibly

(f) a non-mercaptan group containing dicarboxylic acid or an anhydride of such an acid or

(g) a Llonocarboxylic acid, preferably a Monomercaptan monocarboxylic acid, or

(h) a monohydroxy alcohol, preferably a monomercaptan monohydroxy alcohol.

In a corresponding manner, esters can be used which are obtainable by going in any order you want

with each other

Gx) a Monomereaptanmonocarbonsäure or a Monomercaptan-

monohydroxy alcohol,

(i) one at least three alcoholic hydroxyl groups per

Molecule containing compound and

(q) a two, but not more than two, carboxylic acid group

per molecule containing compound.

As would be the case with those skilled in the art of making polyesters known, a carboxylic anhydride can be used instead of the corresponding carboxylic acid is used, while an alcohol can be replaced by a 1,2-epoxy, whereby a Epoxy group corresponds to a primary and a secondary alcoholic hydroxyl group. Substances that contain at least two Carbonsäuregruppeη contain, or anhydrides thereof, the- as Component (c), (f) or (j) can be used e.g. succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, sebacic acid, malic acid, citric acid, tricarballylic acid and pyromellitic acid as well as dimerized and trimerized ethylenically unsaturated fatty acids and their Anhydrides (-if they * exist). Ethylenically unsaturated Although dicarboxylic acids can also be used, they are not preferred.

, 409885/1377

The monomercaptan monocarboxylic acids used as component (a) are preferably thioglycolic and 2- and 3-liter captopropionic acids. The I.ionomercaptan monohydroicyalcohols used as component (a) are preferably 2-kercaptoethanol, 1-mercaptopvOpan-2-ol and 2-Iercaptopropan-i-ol. The monomercaptanedicarboxylic acid (d) is preferably kercaptosuccinic acid (II00CCH ₂ CH (SH) C00H).

Among the substances that have at least two alcoholic hydroxyl groups contain ("b, e, i) include those as already mentioned above as suitable polyhydroxy alcohols for the preparation of the compounds of formula 14 are listed. To mono-1,2-epoxides, which instead of a dihydroxy alcohol May be used include those enumerated above and also glycidyl ethers of alcohols or of phenols, ϊΤ-glycidyl compounds and glycidyl esters of Carboxylic acids. Instead of trihydroxy and higher alcohols, monoepo: QTnonohydroxy alcohols, such as glycidol, or a Diepoxide, such as a diglycidyl ether of an alcohol or a Phenols. Can be used.

It is often useful in the manufacture of a poly mercaptan ester for the use according to the invention, a monofunctional compound such as a monocarboxylic acid (g) or a monohydroxy alcohol (h) as a chain terminator and it is particularly advantageous to use a compound containing a mercaptan group suitable examples are Monomercaptanmonocarbcnsäuren and Monomercaptarmonohyaroxyalkohole and especially thioglycolic acid, 2-mercaptopropionic acid, 2-hercaptoethanol and 2-mercaptopropan-1-ol.

The polymercaptan esters are generally known substances (see e.g. US Patents 2,456,311, 2,461,920, 2,914,585 and 3,138,573, the French

4 0988 5/1377

British Patent 1,503,633 and British Patent 94-1 829) · You can by heating together of the reactances, in the "presence of a catalyst, for example a strong acid (especially an anion exchange resin, of toluene-p-sulfonic acid or 50 "pointer Sulfuric acid) and an inert solvent such as toluene, Xylene, 'trichlorethylene or perchlorethylene, are produced, with the water formed during the reaction as Azeotrope can be removed.

If the shrinkage resistance or the permanent ironing effect (the freedom from ironing) decreases with prolonged exposure to light axif the treated keratin material, it is advisable to incorporate a stabilizer against the disadvantageous influence of light. Examples of suitable stabilizers (component 2) are aromatic compounds with at least one phenolic hydroxyl group and at least one alkyl or alkoxy group with Λ to 8 carbon atoms in the same benzene ring, in particular compounds with 1 to 4 benzene rings, at least one of which is phenolic Carries a hydroxyl group ortho to such an alkyl or alkoxy group.

Appropriate representatives of this component based on the keratinous fiber material are those of the general formulas

Y ^# Y ¹ (29)

wherein B. and Bp are alkyl or alkoxy with 1 to 8 carbon atoms, X ^ alkylene with 1 to 4 carbon atoms, -CO-,

409885/1377

-S- or -0-, Y and Y 'each »hydrogen, hydroxyl or carboxyl, with the proviso that at least one hydroxyl is present in the molecule and m ¹ and m" are integers from 1 to 4; X ^ can optionally be substituted or unsubstituted by lower alkyl or be substituted phenyl;

^C An

where B ^ and B ^ are each alkyl groups having 1 to 6 carbon atoms and n, m ¹ and m "are integers from 1 to 4. The substituents B- and B ^ can be methyl, ethyl, propyl, isopropyl, butyl, tert. The hydroxyl groups are preferably in the ortho or para position to the bridging alkylene group (CnHp _n ), which is, for example, -CHp-, -CHpCHp-, -CHCHp-, -CHpCHpCHpCHp- or -CH- acts. All of them

CH ₃ C ₃ H ₇

Numbers m ¹ and m ″ include the integers 1 to 4, preferably 1 and 2.

Particularly advantageous as component (2) are the connections of the sorts

409885/1377

(31)

HO

CH

(32)

C (CH ₃ )

HO-

α · 2η

C (CH ₃ ). V-OH

(33)

o) o

OH

OH C (CHo)

ι J

'n ⁿ 2n

C (CH ₃ )

wherein η is an integer from 1 to 4, and the Formulas

(34)

(CH ₃ ) ₃ C OH OH C (CH ^)

(CH ₃ ) 3 C

C (CH ₃ )

0 9 8 8 5/1377

(35)

3 OH

CH,

^C 2 ^H 5

C (CH-).

(36) (37)

C ₃ H ₇ C

C (CH ^)

OH-

C (CH ₃ )

(38) (39)

HO

C (CH ₃ ) ₃ C (CH ₃ )

CH C ₃ H ₇

OH

CIL

CH.

C (CH ₃ ) ₃ C (CH ₃ ) ₃

OH

Advantageous stabilizers are those of the formulas

_CH 409885/1377

(41)

(42)

C (CH ₃ ), HO-O <

C (GIU)

t ~> ■

I RO

I.
L.

C (ClI ₃ ).

(43)

(
I.

3'3

SC ₈ H ₁₇

C (CH ₃ )

SC ₈ H ₁₇

(44)

HO

C (CH ₃ )

CH ₂ PO ₃ CH ₂ CH ₃

Ni ²⁺

or those of the formula

OH E

where E is hydrogen, tert-butyl or tert-amyl, E _x . Methyl, tert-butyl or tert-amyl and Ep denote hydrogen or chlorine.

409885/137

These compounds are preferably in organic solvents, z. B. lower alkanols such as ethyl alcohol or methyl alcohol, lower ketones such as ethyl methyl ketone, Benzene, hydrocarbon and halogenated hydrocarbon solvents, especially chlorinated and / or fluorinated hydrocarbons, .the no more than three Contain carbon atoms, such as. B. the dry cleaning solvents Carbon tetrachloride, trichlorethylene and Perchloräthyleη, ethers, like diethyl ether, and esters, · like Ethyl acetate, soluble.

Component (2) represents condensation products of dicyandiamide, Cyanamide ■ or another bifunctional Compound that with a polyamine or a mixture of two or three of these compounds, a polyamine and a spihalohydrin can be condensed. These condensation products are known materials. They are cationic, polymeric and crosslinkable, usually water-soluble and are generally prepared by reacting a polyalkylene polyamine, such as. B. of a poly (ethylene imine) and especially an amine containing 2 to 8 alkylene groups per molecule, sometimes in the presence a base, with spichlorohyarine and subsequent acidification,

This also includes the derivatives of more complex amines. It can in particular amines obtained by heating polyalkylenepolyamines obtained with dicyandiamide with the release of ammonia, poly (arainoamides), which are made from polyalkylenepolyamines and aliphatic dicarboxylic acids or amide-forming derivatives thereof, e.g. B. their dimethyl esters, obtained v / ground, used. Other examples are adducts of polyalkylene polyamines with a stoichiometric one Deficiency (based on one epoxy group per amino hydrogen atom) of mono- or poly-1,2-epoxydeη. The for

409885/1377

use in the method according to the invention is best Suitable condensation products are obtainable by reacting dicyanamide, cyanamide and / or a saturated one aliphatic dicarboxylic acid with 2 to 20, preferably $ to 14 carbon atoms or an amide-forming derivative thereof and a polyalkylenepolyamine having 2 to 8 alkylene groups with a kpihalohydrin, especially spichlorohydrin. .

Examples of aliphatic ^ dicarboxylic acids are oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid. Examples of their amide-forming derivatives are their dimethyl esters, but mixtures of these acids or esters can also be used. One or more polyamines can be used to prepare these condensation products. Specific examples are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine and N, N-bis (3-sminopropyl) methylamine. Suitable amines preferably contain at least 2 amino groups which _{are separated from one another by a hydrocarbon group of the general T formula CH 0} , in which a is at least 2 and at most 4.

The equivalent ratio between those for the condensation products The various starting materials used are preferably such that every equivalent of primary Amino groups of the polyamine 0.1 to 1 mol of dicyandiamide or .0.2 to 2MoI cyanamide and / or another bifunctional Ieη Compound and 0.3 to 3 moles, preferably 1 to 1.5 Moles epihalohydrin for every equivalent of secondary There are no amino groups in the polyamine. Preferred condensation products are obtained by reacting 3 moles of diethylenetriamine, 0.5 to 1 mole of dicyandiamide and 2 moles of dimethyl adipate with 4-, 5 moles of epichlorohydrin.

409 88 5/137 7

The nitrogen-containing condensation products (3) generally dissolve in that present in the treatment bath Water. Many of the polythiols are insoluble in water; however, they can be obtained from organic solvents or in the form of of aqueous dispersions or emulsions in which the condensation products (3) can advantageously be contained, be applied. The organic solvents can be selected from the group mentioned above.

The ones used to carry out the method according to the invention Preparations contain mixtures of components (1) to (3), dissolved in an organic solvent or dispersed or emulsified in aqueous preparations.

The amounts of the various components used in the process according to the invention are 0.5 to 5% polythiol, 0.1 to 1% condensation product (3) and 0.01 to 0.2% stabilizer (2), each based on the weight of the Textile material. A preferred weight ratio between the polythiol and the condensation product (3) is 7.5 to 25: 1.

If no condensation product (3) is used, the reaction of the polythiols with the fiber material can be achieved by curing the polythiol on the material, e.g. B. in the presence of Curing catalysts, are accelerated. At ordinary temperatures, curing takes 5 to 10 days or even even longer. However, the mapping reaction can go through Use of a catalyst can be greatly accelerated and in general the catalyst is preferably the one to be treated Material added at the same time as the thiol applied, although it was also added beforehand if desired or can be added afterwards. The curing time can be adjusted by appropriate selection of a suitable catalyst

409885/137 7.

can be controlled and the choice of curing time depends on the special application of the method according to the invention away. The catalysts can be bases, siccatives, sulfur, sulfur-containing organic compounds and free radicals forming catalysts such as azodiisobutyronitrile, peroxides and hydroperoxides, or combinations thereof.

Primary or secondary amines, such as B. lower alkanolamines, such as mono- and diethanolamine, and lower alkylenepolyamines, such as iithylenediamine, diethylenetriamine, Triethylene tetramine, tetraethylene barrier amine, propane-1,2- and -1,3-diamine and hexamethylenediamine ^ can be used. As inorganic bases, water-soluble oxides and hydroxides, e.g. B. Sodium hydroxide, water-soluble, strongly basic Salts such as trisodium phosphate, disodium tetraborate and sodium carbonate, as well as ammonia can be used. to Sulfur-containing organic compounds that can be used as catalysts include those in which .the sulfur atoms' are not exclusively present as mercaptan groups, in particular mercaptobenzothiazoles and their derivatives, dithiocarbamates, thiuram sulphides, thioureas, disulphides, alkylxanthogen sulphides and alkylxanthates Examples of siccatives (drying oils)! Are calcium, Copper, iron, lead, cerium and cobalt naphthenates. Examples suitable peroxides and hydroperoxides are cumene hydroperoxide, Tert-butyl hydroperoxide, dicumyl peroxide, dilauryl peroxide, Methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate and chlorobenzoyl peroxide. Other suitable catalysts are salts of a heavy detail with an acid with an acid strength (-log K) below 5 or chelates of a heavy metal including chelates, which are also salts. Under "heavy metal" there is such a thing Understand, as revised in Lange's Handbook of Chemistry, 10th Edition, McGraw-Hill Book Co., on pages

■. "-. 409885/137 7

to 61 is designated as "difficult", d. H. a metal from group IB, HB, IHB, IVB, VB, VIB, VIIB or VIII, a metal of group IHA with an atomic number (atomic number) of at least 13, a metal of group IVA with an atomic number of at least 32 or a metal from group VA with an atomic number of at least 51 · Bsi · <iem metal preferably one from group IB, HB, IVB, VB, VIB, VIIB or VIII, especially the first period of these metals, d. H. Titanium, vanadium, chromium, manganese, nickel and especially iron, cobalt and copper. Suitable salt-forming agents Acids are mineral acids, in particular hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, Phosphorous acid. And phosphoric acid, as well as organic Acids, v / ie chloroacetic acid, fumaric acid, maleic acid, oxalic acid, salicylic acid and especially citric acid. Suitable Chelating agents are those in which the chelating atoms are oxygen and / or nitrogen atoms, such as z. B. 1,2- and 1,3-diketones, such as acetylacetone, alkylenediamines, such as ethylenediamine, and especially ethylenediaminetetraacetic acid.

The amount of catalyst used can vary widely. Generally 0.1 to 20, usually 1 to 10 % By weight, based on the weight of the polyol used, required, although much larger amounts can be used. The curing of the polythiol is also assisted by using elevated temperatures and if results are to be achieved particularly quickly, then temperatures can be within the range 30 to 180 ° C can be used. High moisture contents also accelerate the hardening in the presence of Ca celysatoren. Hardening is also promoted by working at a pH within the 7.5-12 range.

409885/1377

The preparations according to the invention can be applied to the fabric by padding or by scooping out, and such a treatment can be carried out before or after dyeing. The methods may be at pH values carried out within the range 5 to 12, preferably from 8 to 11, at temperatures from room temperature (2O ⁰ G) to 100 ⁰ C, preferably between 20 and 40 ⁰ C, and they are usually in the Exhaustion process ended after 1 to 2 hours. - '-

¹ as further components, the surface treatment baths used in this invention (Appretier- or textile finishing baths) can, for example, thickeners, such as' carboxymethylcellulose, surfactants as emulsifiers or dispersants, aminoplasts, salts, acids and the like. The subsequent drying can be carried out for between 80 and 150 ⁰ C, etwa'30 seconds to about 10 minutes at temperatures between 80 and 200 ⁰ C, preferably.

The preparations according to the invention can in the usual way and way on the keratin-containing material or keratin material "rial" be applied. If z. B. Wool sliver or woven fabric are to be treated, they can be padded with it or the material can be placed in a bath containing the agents be immersed. If clothes or items of clothing are to be treated, then it is useful to combine them with the To spray agents, it is even more convenient to place them in a drum with the agents in an organic solvent to hurl; For the latter method, a dry cleaning device using a Dry cleaning solvent is a particularly suitable device.

409885/1377

"The term" keratin-containing material or keratin material "as used here includes all forms of keratin-containing fibers or keratin fibers or fabrics and clothes made therefrom, e.g. fleece, sliver, carded roving, noils, yarns, threads, velor fabrics (terry fabrics ), non-woven fabrics, woven fabrics and knitwear! In most cases the treatment will be applied to fabrics or dresses made from them, although it is also possible and may be desirable under certain circumstances, fibers for example in the form of lace The material to be treated can either consist entirely of keratin-containing fibers or mixtures of these fibers with a synthetic fiber and thread material including polyamides, polyesters and poly (acrylonitrile) and with cellulosic material including regenerated cellulosic material. In general, however, the material should at least 30% by weight of keratin-containing fibers or contain keratin fibers and the best. Effects are achieved with a material consisting of 100% keratin fibers. The keratin-containing material or keratin material (hereinafter always referred to as keratin material for the sake of simplicity) can be untreated or recovered - and this is preferably sheep's wool. However, Ss can also be derived from alpaca, cashmere, mohair, vicunia, guanaco, camel hair and lama or mixtures of these materials with sheep's wool.

After the treatment according to the invention, one obtains independently whether these are used to achieve shrink-proof effects or to achieve non-iron effects (dimensional stability effects) is carried out., fabrics or clothes that are resistant to washing in machines, without that local areas of matting arise, and still retain their original dimensions and shape

409885/1377

maintained. Apart from an excellent grip, this shows treated material also exhibits good wrinkle recovery, which is an important property of many garments is, especially in pants, which have a strong tendency to wrinkle in the areas of the knee and on the back of the knee.

When a shrink-proofing treatment is required, then it is usually convenient to apply the components to the fabric, although, as indicated above, they also on fibers in the form of points or a carding roving can be applied. The shaping "■ (set" ting) 'including the ironing of the fabric can be done independently of whether it (it) is carried out before or after the treatment with the mixture of components (1) to (3) v / ird, be effected by known methods, for example by means of shaping agents such as reducing agents, Bases, water and superheated steam. The most commonly used agent is monoethanolamine sesquisulphite and it can be used in conjunction with a swelling agent such as Urea, can be used. In another method, the material is treated with a swelling agent and an alkanolamine carbonate, z. B. urea and diethanolamine carbonate, impregnated, dried and semi-decated. If desired, the fabric can of course also be in the presence of the agents solidified, so that the solidification (shaping) - and shrinkage treatment performed simultaneously will.

If a non-iron treatment is required, so can this affect the. achieved in various ways. His method is to treat the material with the agents to process the material into garments and using reducing agents, bases or

409885/1377

overheated. Water vapor as shaping agents (solidifying agents) Introduce crevices or tricks. The agents can also be used at any stage during the manufacture of the fabric, for example in the form of tips or yarns to which fibers are applied. If desired, substances which the thiol groups of Block wool, such as B. formaldehyde or higher aldehydes, on the clothes provided with folds or nips after Hardening the polythiol "be applied.

Another method of applying components (1) to (3) (dissolved in an organic solvent) to achieve a no-iron effect is the finished Dress or item of clothing that already has the desired shape, for example the desired folds or tricks has to treat. In this method, it is important that the polythiol be applied in an organic solvent is, because by the treatment with aqueous systems the wrinkles or already present in the tissue Gimmicks were eliminated.

Another method that mainly focuses on making permanent iron-on creases or just creases (pinches) is to treat the fabric with the agents in the area where a fold is introduced is supposed to give it the desired shape and to keep it in this shape with the application of heat and pressure.

A method of ironing flat and shrink-proofing Keratin fabric consists of the fabric with a solidifying agent (Shaping agent) and treat it by heating the still moist tissue in a flat To bring it into shape, to impregnate it with an aqueous emulsion or dispersion of the agents, to the fabric

4 09885/137 7

2A29062

dry and harden the polythiol. Eventually that will Fabrics made into clothes and in these are desired enf a Ils by treatment with steam in the presence a solidifying agent such as monoethanolamine sesquisulphite, Creates creases or folds.

The keratin material which has been surface-treated according to the invention also has excellent and permanent resistance to the adverse effects of light. In addition, the finishes can also reduce the mechanical properties, e.g. For example, the tensile strength, elongation at break, the wear resistance and pilling-l \ ^T tilt of the treated keratinous material, improve.

_v The invention will be explained in more detail with reference to the following examples. Unless otherwise stated, all parts and percentages therein relate to weight and the temperatures are stated ^{in ° C.} The polythiols used were made as follows:

Polythiol A.

A mixture of 8QO g (0.2 g-mol) of a triol with a average molecular weight of 4-000, made from glycerine and propylene oxide, 55 * 2 g (0.6 g-mol) thioglycolic acid, 5 g of toluene-p-sulphonic acid and 350 ml of toluene was heated to reflux with stirring in a nitrogen atmosphere. The water formed during the reaction (10.8 ml, 0.6 g-mol) was removed in the form of an azeotrope with toluene. The mixture was cooled and washed with water and the organic layer was separated. After removing the solvent from the organic layer under vacuum Remaining 793 g (theoretical yield 94%) of the desired

.. "" 409885/1377

- 52 -

Tris (thioglycolate) with a thiol content of 0.59 equiv / kg return.

Polythiols B and G

These were made from glycerine / propylene oxide adducts with a respective average molecular weight from 600 and 4-800, spichlorohydrin and sodium sulphide manufactured poly (2-hydroxy-3-mercaptopropyl) ether. The products had a mercaptan content of 3.7 equiv / kg and 0.32 equiv / kg, respectively.

Polythiols D-S

These polymercaptan esters are as described for polythiol A. produced, in the case of the resins J-S. instead of toluene perchlorethylene was used and im In the case of resins D-I, the reaction mixture was not washed with water: any unreacted Mercapto acid was made along with the remaining toluene (or perchlorethylene) by stripping the product under Vacuum removed in a rotary evaporator. The materials used to make these polythiols are in given in Tables I and II. No catalyst was used for Resin P.

Polythiols T and U

It was poly (2-hydroxy-3-mercaptopropyl) ether, which resembled polythiols B and C. The polythiol T contained two to three -SH groups per molecule, its thiol content was 1.4 nq / kg and its molecular weight was within the range of 1500 to 2000. The polythiol U

4Ö9885 / 1377

contained about three -SH groups per molecule, its thiol content was 0.54 eq / kg and its average molecular weight was about 3000.

. Polythiol V

A mixture of 500 g polythiol B, 218 g (2.37 eq.) Thioglycolic acid, 1.5 g toluene-p-sulphonic acid and 500 ml Perchlorethylene was refluxed under nitrogen for 8 hours, the amount formed during the reaction Water (44 ml) was entrained. After the mixture was washed with water until its pH was 5 to 6. the solvent was stripped off in vacuo. The residue (640 g) had a thiol content of 5.7 eq / kg and egg? contained five to six thiol groups per molecule.

Polythiol W

A mixture of 529 g polythiol C, 19.5 g (0.212 iiqu.) Thioglycolic acid, 1 g of toluene-p-sulphonic acid and 350 ml of perchlorethylene was heated as indicated above, forming 4 ml of water. The mixture was made with a slurry stirred by 5g sodium bicarbonate and 2.5 ml water, filtered and stripped in vacuum. The residue (532 g) had a thiol content of 0.58 eq / kg and contained five to six thiol groups per molecule.

Polythiol X

This was prepared as described above for the polythiol V. from '500 g of polythiol T, 89 g of thioglycolic acid, 4 g of toluene-p-sulphonic acid and. 500 ml perchlorethylene; there were

409885/1377

23 ml of water carried along. The residue had one Thiol content of 1.78 eq / kg and contained five to six Thiol groups per molecule.

Polythiol Y

This was prepared as described for the Εθ-lythiol X, this time, however, 500 g of polythiol U and 36.4 g Thioglycolic acid were used. The residue had a thiol content of 0.75 eq / kg and contained five to six Thiol groups per molecule.

409885/1377

ft Polythiol ■, Name of the
Manufacturer Table I. . made
11 j.
Alkylene QXyd lit off
Alcohol or
Amine - esterifying
acid ι Φ · '
N)
CO D. Caradol 3000 PO Glycorol Thioßlycol- '■ Ul O
CD
N) E. Caradol 5001 PO with EO-Eno ti 1 * ^ ■ '■
σ.
co
OO P. Polyurax G 1000 p ₀ group ti 11 OD
cn. G
; η Polyurax G 3000
Polyurax G 3521 Polyol adducts PO
EO / PO (10:90) ti
M. »
11 I. Polyurax G 1000 byscb
Molecu
lar wt. PO ti 2-mercapto
propion ~ co J Caradol 5001 3000. PO with EO-Enc _ ti Thiοglycol K Polyurax G 1000 5000 p ₀ group η η L. Voranol CP 700 1000 PO It It H Caradol 3000 3000 ..
3000-
4000 PO H H • N ITiax LKT 112 1000 PO Hexane -1,
2,6-triplet η 0 Polyurax G 4000 5000 PO Glycerin 2-Mcrcapto-
propionic 1000 700 3000 1500 4000

Continuation of the table on page 35a

Name of the
Manufacturer Polyol adduct η. ^her ' ^c
Alkylene oxide made out
Alcohol or
Amine esterifying
acid Polythiol Pluracol EDP 500 through
Molecu
lar wt.
("MG) PO Athylon _.-
diatiin Thioglycol
acid P. 500 PO Pentaery
thrit ' η Q Pluracol TP 4040 2220 ' PO Trimothylene
propane η R. Polymog 1000 4040 Tetrahydro
furan Butane -1,4-
diol η S. 1000

EO «ethylene oxide

PO = Pro pylon oxide '

"CARADOL", "POLYUHAX", "VOHAWOL", "STIAX", "PLURACOL" and "POLBIEG" are trademarks; the "OARADOL" products are available from the company ühell Chemical Co., the ¹ TOLYURA ¹ X "products are available from the company BP Chemicals Ltd., the" V0RAN0L "product is available from the company Dow Chemical Co., the "ΝΙΛΧ" product is available from Union Carbide, the "PLURA0OL" products are available from Wyandotte Chemical Corp. and the product "POLYMEG" is available from The Quaker Oats Co. The for Production of the thiol resin Q The polyol used was produced in a known manner by reaction in the presence of sodium hydroxide.

O*

K)

N) CD O

Table II

Polythiol Component ^
substance L.
Io Ver
ratio Thiol content
(A- equiv./icg) ^ ■■■ '': glycerin
Adipic acid
Butane -1,4-diol
Thioglycolic acid 1
4th
4th
3 2.35 ' ^B l trimerized linoleic acid *
Poiyol I
Thioglycol säui-e - 1
3
3 1.09 . ' ^c i '■■;. ■; ■; Polyol II
Mercap tob ernst einsäur e
nrBentanol , i
3
3. .0.83 Polyol II
Adipic acid
2-iercapto & ethanol 1
3
.3 .. 0.62 ' ^E l ■', Polyol III
Mercap raging one acid
Thio gly cols acid e 3
2
2 1.15 Hexane: -1, 2,6-triol
• diicerisLerte linoleic acid **
Hexane -1,6-diol
Ohioglycolic acid _ 1
5
4th
2.5 0.94 V ■ - .. '■ tri-ruptured linoleic acid
Butane -1,4-diol
Thioglycolic acid. 1
3
3 1.64 H ₁ - Polyol IV
A dipic acid "e
Butane -1,4-diol
ihio glycolic acid 1
3
3
3 1.78 - " Hexane -1,2,6-triol
dimerized linoleic acid
Pplyol I.
Thioglycolic acid 1
2
2
3 0.99

A09885 / 1377

Polythiol ^L l Components
substance IvIo 1 ver
ratio Thiol content;
(- quiv. / kß) ^K l ^M l Glycerin
Adipic acid
Polyol V
Thi (»glycolic acid 1
2
2
3 2.07 . ^N i 1,1,1-tri _m ethylolpropan
B er ns te ins aur e
mixed diOrimary alcohol
hole ** = *
Ehioplvcoisaure 1
4th
4th
3. 0.82 ⁰ I. trinerized linoleum acid
Butane · 1,4-diol
3-L! Er cap top rop i ons äur e 1
3
3 2.11 ^P l 1,1,1-triine thyolpropane
Adipic acid
Poiyoi ι
3-Iusrcaptopropionic acid 1
2
2
3 1.95 Q ₁ 1.1, l-trim thy lolpropane
Adipic acid
2,2-ice (jg-hydroxypropoxy) -
phenyl) ρropane
Th io glycolic acid 1
2
2
3 1.63 ^R l Glycerin
Adipic acid '
Polyol IV -I '
Thioglycolic acid. " 1
4th
•
4th
3 1.10 Polyol IV
. Adipic acid
2,2-ice (p_-hydroxypropoxy) -
; phenyl) propane
Thioglycolic acid . 1
3
3
3 1.36 trimerized linoleic acid
Polyol "VI
Thiogly colic acid 1
3
3 0.85 Amber acid anhydrite!
■ 2-Ajercap to ethanol 1
3
3 0.48,

/. ηοββς / 1277

Polythiol ό, .. "■" component
SubetanZ ^ vlolver-
age Thiol content
(i, equiv. / kg) .T ₁ Polyol VII
- Dinersed linoleic acid
2 - 'iercaptoSthanol 1
A.
A. V Glycerin
Pht h as ätu? e ank ^ dr i d '
Butane -1,4-di'ol
Thioglycoic acid 1
A.
A.
3 > olyol VIII
M / er cap tob serious into acid 11
10 0.40 W ₁ 'Polyol I.
Mercaptor Amber 11
10 1.65 : ^x i Butane -1,4-diol
Mercaptic succinic acid 6th
5 3.98 raised diprimary alk
M er cap tob ernst e ins airr e
Thioglycotic acid Ie 2
1
2 1.79 ² I. 'Polyol I.
II. Ercaptobernsteinsäuxe
Adipic acid
acetic acid 11
6th
A.
2 0.93

409885/1377

Footnotes:

* The triiaerized linoleic acid with an average molecular weight of about 800 and a carboxyl content of about 3/1 equivalents / kg was sold by Unilever-Emery Ή.Ύ. , Gouda, Holland., Under the name .- "Trimer acid Smpol 104-3 "received.

** The dimerized linoleic acid obtained under the name "Dimer acid Esrpcl 1022" from the same company had an average molecular weight of about 570 and a carboxyl content of about 3.4 equivalents / kg.

*** The mixed diprimary alcohols having an average molecular weight of about 7OO and a hydroxyl value of 155 reported to 165, and w ^r ere prepared by catalytic hydrogenation of Methylestern of long chain aromatic-aliphatic fatty acids, which are to Diels-Alder adducts of Styrene with ethylenically unsaturated acids such as linoleic acid. _(Acted. The alcohols were obtained under the name "Comerginol 65" by the company Bibby Chemicals Ltd., Liverpool, England.

"Polyol I", "Polyol III" and "Polyol VIII" were Pol; Coxypropylene) glycols with an average Molecular weights of 425, 1000 and 2000, respectively.

"Polyol II" and "Polyol IV" were glycerine-propylene oxide adducts with an average molecular weight of 700 and 3OOO, respectively.

"Polyol V" and "Polyol VI" were poly (oxyethylene) glycols with an average molecular weight

409885/1377

weight from 400 or 500.

"Polyol VII" was a pentaerythritol-propylene oxide adduct with an average molecular weight of 650.

409885/137 7.

Component (3)

I. It was a reaction product of a poly (amino amide) prepared from diethylenetriamine and Adipic acid, with epichlorohydrin, made as in Example I of U.S. Patent 2,926,154. It was used in the form of an aqueous solution containing 10% by weight of resin-forming materials (condensation product (I)) included.

II. 3 moles of diethylenetriamine were heated first with 1 mole of dicyandiamide and then with 2 moles of dimethyl adipate. This reaction product was then heated with 4-5 moles of epichlorohydrin, and the resin was finally diluted with water so that a 20 volume solution of the condensation product II was obtained.

III. In 37 S isopropanol dissolved and heated ^{to 88 ° C.} Then 24.7 g of a poly (aminoamide), prepared from polymerized linoleic acid and diethylenetriamine (0.1 amino group equivalent), dissolved in 15 S isopropanol, were added dropwise to the spoxyd solution. The mixture was then stirred under reflux for 5 hours and 1.85 g of epichlorohydrin was added. 16 g of glacial acetic acid were then added in 312 g of water and the mixture was stirred until it had cooled. A liquid with a low viscosity was obtained, which had a content of the condensation product III of 20 - / o and a. pH 4.6.

409885/1377

The emulsions containing the polythiol were prepared by dissolving 0.5 parts of sodium carboxymethylcell.ul.ose in 44-, 5. Share water at '/ 0 to 80 ⁰ C, cooling down. let the solution, .Addition of 50 parts of the polythiol and 5 parts of a solvent (an adduct of p-nonylphonol and 9 "mol of ethylene oxide) and five-minute stirring in a high-speed mixer.

■ Example 1

A Wol.lgewe-be (100% wool) -. Was, at room temperature with impregnated with the following aqueous preparation:

90 parts of polythiol A (40% aqueous emulsion)

1 part of the compound of the formula (59) dissolved in

• 50 parts of p-chloroethylene

12 parts of condensation product II (20% aqueous

. .Ge solution) of component (5)

2 parts of adduct of 9 mol of ethylene oxide and 1 mol . p-Tert.-nonylphenol (75% aqueous

Solution)

20 parts of sodium carbonate

875 parts V / water

1000 parts

After the fabric had been impregnated and squeezed (up to a weight increase of 80 %) , it was dried at 110 to 150 ° C. for 2 to 4 minutes. It is important that the fabric is completely dry or slightly over-dried. For this reason, the drying temperatures and the drying time can be varied as required so that the absolute dryness of the fabric can be guaranteed.

409 885/137 7

M 4

The treated tissue met the condition of I. V /. See Specification 12. “When the G-ev / ebe was exposed to daylight (e.g. under glass), no change in the non-matting effect occurred, even after an exposure intensity of 4-000 Langley units. When the same test conditions were used without applying the compound of formula (39), there was a sharp deterioration in the non-matting effect after this exposure (e.g. a 2% shrinkage before exposure, a 4-0% some shrinkage after exposure). Similar effects were obtained when the compounds of the formulas (36) and (37) were used as stabilizers or the condensation product I of component (3). were used.

Relaxation shrinkage (IWS specification 72): 500 g of the samples were placed in a "Cubex" laboratory washing machine. The entire filling in the T.iaschine for 3 hours in 7.5 1 of phosphate buffer (pH 7), heated to 4-0 ⁰ C (wash / fleets ratio 1:15)> and centrifuged for 10 seconds. The samples were then smoothly dried in an oven at 70 ⁰ C and 16 hours conditioned at a temperature of 20 ⁰ C and a relative humidity of 65%. The dimensions of the fabric were measured before and after washing and the linear shrinkage in length and width was calculated. The area shrinkage was calculated from the changes in the linear dimensions.

Example 2

A woolen fabric was impregnated at room temperature with the aqueous preparation specified below and squeezed out to a weight increase of 100%:

409885/1377

80 parts of folythiol A (4-0% aqueous emulsion)

0.8 part of compound of formula (37)

10 parts of condensation product III (20 # aqueous Solution)

3 parts of an adduct of 14 moles of ethylene oxide and 1 Molp-Tert.-nonylphenol (50% aqueous Solution)

10 parts of sodium carbonate made up to 1000 parts with water.

The samples v / ere then at 80 ° C and then about 2 minutes, dried at 110 ⁰ C. The treated fabric met IWS specification 72. No change in non-entangling effects was observed with each exposure to light (e.g. 4000 Langley units). The non-entangling properties of a sample which had been finished (surface-treated) with the above-mentioned preparation which did not contain any compound of the formula (57) did not pass the IV / 8 test after exposure to light.

' Example 3

A woolen fabric was impregnated at room temperature with the preparation given below and except for an increase in weight squeezed out by 100%;

3% polythiol A 0.15 % of the compound of the formula (44) 0.6 % diethylenetriamine in 1000 parts of trichlorethylene.

The percentages relate to the weight of the treated Tissue. The treated tissue was then at

• 409885/1377

100 ° C dried. Samples of this fabric were taken before and after tested for exposure to light (4000 Langley units) and met IWS Specification 72.

Example 4

A woolen fabric was impregnated at room temperature with the following aqueous preparation and to o squeezed to a weight increase of 100 ° /:

90 parts of polythiol B (40% aqueous emulsion)

1 part of the compound of formula (36)

2 parts of an adduct of 9 moles of ethylene oxide and

1 mol of p-tert-nonylphenol (75% aqueous Solution)

20 parts of sodium carbonate, 887 parts of water

1000 parts

The treated fabric was then dried at 80 ⁰ C and then for 4 minutes at 120 ° C. It passed the IVifS Specification 72 test before and after exposure to light.

According to the invention, the other abovementioned polythiols can also be used and stabilizers can be used in a corresponding manner.

409885/1377

Claims (1)

Claims 1. Process for modifying keratinous material or keratin material, characterized in that one treated the material with an organic solution or an aqueous emulsion containing: 1) 0.5 to 5 wt.? 6, based on the weight of the keratin material, Polythiols with at least two thiol groups per molecule and a molecular weight between ■ “AOO and 20,000, which are the reaction products from a) polyalcohols, b) alkylene oxides and / or dicarboxylic acids, C ^) carboxylic acids containing thalol groups or Cp) epihalohydrins and alkali hydrogen sulfides (whereby these folythiols may contain ether and / or ester bonds) or of a ^) polycarboxylic acids, - b ^) alkylene oxides or dialcohols and Carboxylic acids containing C-) thiol groups acts, \ 2) 0.01 to 0.2% by weight, based on the weight of the keratin material, of monomeric stabilizers against the adverse effects of light, and 3) optionally 0.1 to 1% by weight, based on the weight of the keratin material, of condensation products of d) Dicyanaiaraid, Cyanamid or some other bifunctional cell Compound or mixture of two or three of these components,
■ --- e) one at least three primary and / or secondary 409885/137 7 Polyamines containing amino groups and f) a spihalohydrin, and that the treated material is dried and, if necessary, cured. 2. The method according to claim 1, characterized in that the material is treated with an organic solution or an aqueous emulsion containing 1) 0.5 to 5 weight 70, based on the weight of the keratin material, of polythiols with at least two thiol groups per molecule and a molecular weight between 4-00 and 20,000, which are reaction products from a) polyalcohols, b) alkylene oxides and C _x ,) carboxylic acids containing thiol groups or c2) epihalohydrins and alkali hydrogen sulfides, 2) 0.01 to 0.2% by weight, based on the weight of the keratin material, of monomeric stabilizers against the adverse effects of light, which are are aromatic compounds with at least one sterically hindered phenolic hydroxyl group, and 3) optionally 0.1 to 1% by weight, based on the weight of the keratin material, of condensation products of d) dicyandiamide, cyanamide or another tifunk-. functional compound or a mixture of two 40 9 8 85/1377 or three of these components, e) one at least three primary and / or secondary Amino groups, containing polyamines and f) an epihalohydrine, and that the treated material is dried and optionally hardens. 3. The method according to claim 2, characterized in that one the keratin material 1) with polythiols with at least two thiol groups per : Molecule and a molecular weight between 4-00 and 10,000, which are reaction products of a) polyalcohols, b). Alkylene oxides and "Cyi) carboxylic acids containing thiol groups or Cp) epihalohydrins η and alkali hydrogen sulfides acts, and 2) with stabilizers against the adverse effects of light on the basis of aromatic compounds, which contain at least one sterically hindered phenolic hydroxyl group, treated and the treated material hardens. 4-. Method according to claim 2, characterized in that one the keratin material 1) with polythiols of the general formula [(O-A.Lkylen) OH], [R] ^m V ¹ ■ [(0- / Ikylen) _m 0 (C0) _{w χ} Χ] 409885/1377 wherein πι is at least 1, and in each of the O-alkylene chains has the same or different values, w 1 or 2, ρ at least 2, (ρ + q.) an integer of 3 to 7, each alkylene group being a chain with at least two and at most six carbon atoms between successive oxygen atoms contains, R one aliphatic radical containing at least two carbon atoms and X one at least denote a thiol group and an aliphatic radical containing 1 to 18 carbon atoms, 2) with stabilizers against the adverse "influences from laughs to the general formula wherein B. and Bp are alkyl or alkoxy with 1 to 8 carbon atoms, X ^ alkylene with 1 to 4 carbon atoms, -CO-, -S- or -0-, Γ and Y 'are each hydrogen, hydroxyl or carboxyl, with the proviso ö.aä at least one hydroxyl is present in the molecule, and m ^f and m "are integers from 1 to 4 and Condensation products of d) Dicyandiamide, cyanamide or another bifunctional A compound or a mixture of two or three of these components, e ¹ ) a polyalkylenepolyamine which, in addition to at least two primary amino groups, contains at least one secondary amino group, and 409885/1377 f) a spihalohydrin treated, 5. The method according to claim 2, characterized in that the keratin material with a reaction by one Polyhydroxy alcohols with an alkylene oxide and then Treated esterification of the terminal hydroxyl groups with a mercaptocarboxylic acid produced polythiol. 6. The method according to claim A-, characterized in that the keratin material with a polythiol of the general Formula · treated [R ₁ I [(0-alkylene) _MQ1 [(O-alkylene) _m O, CO, C _u H _2u SH] _pl wherein E ^ is an aliphatic hydrocarbon radical with up to 6 carbon atoms means any alkylene group a chain with at least 2 and at most 6 carbon atoms between successive oxygen atoms contains, m is at least 1 and in each of the -O-alkylene chains has the same or different values, p ^ is an integer from 2 to 6, (p ^ i + q) is an integer from 3 to 7 and u are 1 or 2. 7. The method according to claim 4, characterized in that one the keratin material with a polythiol of the general Formula treated 409885/1377 [(O-A.lkylcn ^ OH] ^ T (O-alkylene) OCH ₀ CHCH ₀ SH] ^{IA J} 'm 21 2] R ₃ " where R is an aliphatic radical with at least 2 carbon atoms, each alkylene group contains a chain with at least 2 and at most 6 carbon atoms between successive oxygen atoms, Ii ₅ , an Eesr from the group -OH, - (O-alkylene) -OH, and - (O-alkylene ^ -0-CO- ^ H ^ -SH means, where ν is an integer of at least 1 and u is 1 or 2, m is at least 1 and in each of the -O-alkylene chains are the same or different has, ρ at least 2 and (p + q) an integer from 3 to 7 mean. 8. The method according to claim 6, characterized in that the keratin material is treated with a polythiol of the general formula [O-alkylene where R ₂ denotes an aliphatic hydrocarbon radical with at least 2 and at most 6 carbon atoms, each alkylene group contains a chain with at least 2 and at most 6 carbon atoms between successive oxygen atoms, m at least 1, Pp a whole. Number from 3 to 6 and u 1 or 2. 9. The method according to claim 7 »characterized in that the keratin material with a polythiol 4 0 9 8 8 5/1377 general formula treated OH where S _{2 is} an aliphatic hydrocarbon radical with at least 3 and at most 6 carbon atoms, α is at least 1, Pp is an integer from 3 to 6 and t is 2 or 3. 10. The method according to claim 7> characterized in that the keratin material with a polythiol resin
general formula treated (OC _t H ₉ ) OCH ₀ CHCH-SH OCOCH ₀ SH wherein Rp is an aliphatic hydrocarbon radical with at least 3 and at most 6 carbon atoms, m at least 1, ρ- an integer from 3 to 6 and t 2 or 3 mean. 11. The method according to claim 8, characterized in that the keratin material with a polythiol one of the
the following general formulas CH 409885/1377 and CH ₀ - (OC.H _0h ) O «CO-e H ₀ SH T 2 ^v C 2t ^y mu 2u CH ~ (OCH ",) O'CO-C H ₀ SH I ■ t 2trm ·. u 2u CH WlIn ^SH where m is at least 1, t is 2 or 3 and u is 1 or 2. 12. The method according to claim 9, characterized in that one the Keratinmaterxal with a polythiol of the general Formula treated CH ₀ (OC O
_O H,) OCH ₀ C ₀ H, -) OCH ₀ OH HCH ^ SH OH _ "(OC ₀ HJ OCH ₀ CHCH ₀ SH OH CH ₀ (OC ₀ H,) OCH ₀ CHCH ₀ SH Z 5 ο m ZZ where m is a positive integer that is a molecular weight within the range of 700 to 6000. 15. The method according to claim 10, characterized in that the keratin material is treated with a polythiol of the general formula 409885/1377 CH ₀ - (OCoH.) OCH ₀ CHCH „SH Z ο ο m ZZ ₀ Z .) OCH ₀ CHCH „ο m Zi Z OCOCH ₂ SH CH - (OC ₀ H.) OCH ₀ CHCH ₀ SH J 'ο tn Zi ζ s OCOCH ₂ SH CH ₀ - (0C ₀ H,) OCH _n CHCH ₀ SH Z ^v J ο m l \ L OCOCH ₂ SH wherein m is a positive integer that weighs one molecular weight within the range of 700 to 6000 V * '"- has. 14. The method according to claim 11, characterized in that the keratin material is treated with a polythiol of the general formula CH _- (OC ₀ H,) OCOCH ₀ SH \ L Jörn Z CH - (OC ₀ H.) OCOCH ₀ SH CH ₉ - (OC ₀ H.) OCOCH ₀ SH ZJ ο m Z where m-is a positive integer that represents a molecular weight within the range of 1000 to 6000. 15. The method according to claim 1, characterized in that a polyester of the general type is used as the polymer thiol Average formula used W JL (0) CO (O) Z (O) CO (O) YSlA V ^ ^r 4 4 ^r / 409885/1377 where q and r, which are not the same, are O or 1, ρ is one positive integer not exceeding 6, Z is a divalent organic radical that has one or more of its Carbon atoms to the specified -0- or -CO -inunities is bonded, Γ a divalent organic radical that has one or more of its carbon atoms is bonded to the indicated -SH-G group and the indicated -0- or -CO units, and W is an organic Remainder mean, the at least one -SH-group contain muli, if ρ = 1, which by one or more its carbon atoms to the specified -0- or -CO-Sin units is bound. 16 .. The method according to claim 15 _5, characterized in that the polythiol used is one which has essentially one of the following formulas 13 ~ 11 15 "I. R Jj-O-CO-R - CO-OR SHJg 13 r 12 16-1. ■ R - [- CO-OR * 0-CO-R- SHj _s 13 r _r 11 12 "1 1Λ R 10 4- CO-R '-CO-O-R -0 4- CO-R- "SH 13- Γ 12 11 η 15 "1 R X C04- 0-R * "-0-CO-K CO 4- 0-R SH LL Jt Js 13 Γ Γ 11 12 η 11 15 Ί R "4 0 + CO-R -CO-O-R- -0 -KPO-R COO-R SHJ 13 Γ Γ -12 11 τ 12 16 Ί R .. CO.! - 0-R- -0-CO-R'-CO 4- 0-R OCO-R 'SH Π I -R- -CO 4- 1.2 14 1 H 4- 0-R- --0-CO-R- -CO 4- OR 'OH JS <a ¹² y Γ W 12. 1 HSR ¹⁶ -CO-OR '-0 - \ COR "' COOR 0 -4- COR * SH L Jt 409885/137 11 in which B. the after, the removal of the two -COOH- : Groups remaining residue of an aliphatic, cyclo- 12 aliphatic or aromatic dicarboxylic acid, R den after the removal of the two remaining hydroxyl groups Best of an aliphatic, araliphatic oaer ■ 13 .cycloaliphatic diol, R one at least two Organic radical containing carbon atoms whose carbon atoms are directly linked to the specified Ester chains -connected with a terminal mercaptan, R the remaining after the removal of the -COOH groups Remainder of a mercaptan group-containing aliphatic, cycloaliphatic or aromatic dicarboxylic acid, t is an integer of at least 1, s a 15th integer of at least 2, R ^ SH den after removal an alcoholic hydroxyl group remaining residue of a monomer aptane monohydroxy alcohol and R ° 8H mean the residue of a monomercaptan monocarboxylic acid remaining after a carboxyl group has been removed. 17- · Method according to claim. 16, characterized in that the polythiol used is one which essentially has one of the following formulas 13 T 11 -ι OCO-R- -CO-O-C H-SH ^{m 2m} J s 13 Γ 12 R-J__ CO-O-R -O-CO-CH ,,. 13th 13th J 2y • CO-R -CO-O-R -O 0-4- CO-R ^ CO-O-R ^ -O- CO-C CO-R -COOC , Jt ^{m 2m} 0 9 8 8 5/13 7 7 R ¹³ Jl C0-t-0-R ¹² -0-C0-R ¹ - ( HS-CH -C0-C ~ R ¹² -0 - [12 -ι -HO-R ^- -0-CO-C..H .SH O-R - O-CO-CII CKCO-J- ΐ J SH OR ¹² OH , 12 CO-CH ₂ CKCO-OR "0-r- CO-CH ^ .SH SH 11 12 1 "5 wherein R, R, R, s and t are as defined in claim 16 and j is 1 or 2 and m is 2 or 3. 18. The method according to claims 16 and 17, characterized in that 11
indicates that R (a) is a saturated al ^ phatic hydrocarbon group with 2 to 10 carbon atoms, which can carry an -SH group, (b) a cycloaliphatic-aliphatic hydrocarbon group with 5 to 3 ^ carbon atoms die.eine äthyienische insätciguig can contain , or (c) represents a mononuclear arylene hydrocarbon group having 6 to 12 carbon atoms. 19 · Method according to claims 16 and 17, characterized in that 12th indicates that R is a saturated aliphatic hydrocarbon chain with 2 to 250 carbon atoms, those substituted by methyl and -SH groups and by ether oxygen atoms and carbonyloxy groups can be interrupted. 20. The method according to claims 16 and 17, characterized in that 1 '6
indicates that R, when attached directly to an -O- unit, is a saturated aliphatic 409885/1377 Hydrocarbon chain with 2 to 250 carbon atoms, those substituted by methyl and -SH groups and interrupted by ether acid atoms and carbonyloxy groups can be, and when it is attached directly to a -CO unit, (a) a saturated aliphatic Hydrocarbon group with 2 to 10 carbon atoms which can carry an -SH group, (o) a cycloaliphatic-aliphatic Hydrocarbon group with 5 up to 51 carbon atoms, which have an ethylenic unsaturation may contain, or (c) a mononuclear arylene hydrocarbon group having 6 to 12 carbon atoms can mean « 21, method according to claim 20, characterized in that the polythiol is the tris (thioglycolate) of polyoxypropylenetriols with an average molecular weight of 600 to 4-000, a glycerine / propylene oxide - Adduct with terminal ethylene oxide and an average Molecular weight of 5000, of a hexane-1,2,6-triol / propylene oxide additive with an average molecular weight of 1500, a 1,1,1-trimethylolpropane / propylene oxide adduct with an average Molecular weight of 4040, the bis (thioglycolate) of an adduct of butane-1,4-diol and tetrahydrofuran having an average molecular weight of 100 or a polyoxypropylenetriol with an average molecular weight of 4,000, · the tetrathioglycolate of an adduct of pentaerythritol with Propylene oxide with an average molecular weight of 4-000 or an adduct of ethylenediamine with Propylene oxide with an average molecular weight of 500; the tris (2-mercaptopropionate) one Polyoxyprcpylenetriols having an average molecular weight from 4000; a poly (2-hydroxy-3- 409885/1377. mercaptopropyl) ether of a polyoxypropylenetriol with an average molecular weight of 4,800; a mercaptosuccinic acid unit and butane-1,4-diol or a polyoxypropylene glycol containing polyester; a unit of thioglycolic acid with a polyoxyethylene glycol, polyoxypropylene glycol, butane-1,4-diol or diprimary alcohols produced by the catalytic hydrogenation of methyl esters of aromatic aliphatic Fatty acids as alcohol component and trimerized linoleic acid or mercaptosuccinic acid as Acid component-containing polyester; a unit of 2-liter iercaptoethanol with a pentaerythritol / propylene oxide tetrol adduct or a polyoxypropylenetriol as the alcohol component and adipic acid, succinic acid or a polyester containing dimerized linoleic acid as the acid component, 5-mercaptopropionic acid with butane-1,4-diol and a trimerized linoleic acid, thioglycolic acid or 3-mercaptopropionic acid with two alcohols η j from elected. from the group glycerine, butane-1,4-diol, Hexane-1,6-diol, hexane-1,2,6-triol, the polyoxypropylene triols, Polyoxypropylene glycol, 1,1,1-trimethylolpropane, those produced by the catalytic hydrogenation of methyl esters of aromatic-aliphatic fatty acids mixed diprimary alcohols, 2,2-bis (phydroxypropoxyphenyDpropane and an acid from the group consisting of adipic acid, dimerized linoleic acid, phthalic acid or succinic acid; one unit of a polyoxypropylenetriol with polyester containing iiercaptosuccinic acid, which is terminated with n-pentanol, or one unit of polyoxypropylene glycol, Mercaptosuccinic acid and adipic acid-containing polyester terminated with acetic acid is used. * anη polyester of 409885/1377 22. The method according to claim 1, characterized in that dai a stabilizer of the general formula is used OH OH ^C n ^H 2n - (_ wherein B ^ and B ^ are alkyl groups having 1 to 6 carbon atoms, which are optionally substituted by lower alkyl or phenyl, and n, m ¹ and m "are integers from 1 to 4. 23. The method according to claim 1, characterized in that • a stabilizer of the general formula is used Y OH
"V CO -f \ wherein B ^ and Bp are alkyl or alkoxy with 1 to 8 carbon atoms, Y hydrogen, hydroxyl or carboxyl and m 'and m "represent integers from 1 to 4. 24. The method according to claim 1, characterized in that a stabilizer of the general formula is used 409885/1377 wherein B _x , and Bp are alkyl or alkoxy groups with 1 to 8
Carbon atoms, Γ hydrogen, hydroxyl or
Carboxyl and m ¹ and m "are integers from 1 to 4. 25. The method according to claim 22, characterized in that a stabilizer of the general formula is used OH OH where B, - and B, - alkyl groups with 1 to 4 carbon atoms, nu and nip 1 or 2 and η is an integer of 1
to 4 mean. 26. The method according to claim 25, characterized in that a stabilizer of the general formula is used where η is an integer from 1 to 4. 27. The method according to claim 25, characterized in that a stabilizer of the general formula is used C (CH ₃ ) 409885/13 77 WOTin η is an integer from 1 to 4. 28. The method according to claim 25, characterized in that a stabilizer of the general formula is used (CII ₃ ) ₃ C OH OH. C (CH ₃ ) ₃ . "IC (CHO ,. where η is an integer from 1 to 4. 29. The method according to claim 22, characterized in that 1,1-3is (3-tert-butyl - ^ - hyäroxy-ömethy! phenyl) butane is used as a stabilizer, 1,1,1-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane or 1,1-bis (3-tert-butyl-4-hydroxyphenyl) butane verv / ends. 30 * na ^method: ch in claim 29, characterized in that one uses a stabilizer of formula C (CHo) ^ C (CHo) o U J- HO -f \ ~~ S f ~ \ - OH ch7 31. The method according to claim .1, characterized in that as a stabilizer octadecyl-3- (3, 5-di-tert-butyl - ^ - hydroxyphenyl) propionate, pentaerythrityl-tetrakis- (3- ■■ "(3, .5-cLi-tert. -butyl-4-hydroxyphenyl) propionate ') or. uses the nickel grain complex of the formula . 409885/1377 υ Η Ni ² ® j
HQ- / V CH ₂ PO ₃ CH ₂ CH ₃ C (CH ₃ ) ₃ 52. The method according to claim 1, characterized in that the condensation product (3) is one is, which consists of a polyalkylene polyamine with 2 to 8 Alkylene groups, dicyandiamide and epichlorohydrin has been. 33 · Method according to claim 32, characterized in that the condensation product (3) is one which consists of a polyalkylenepolyamine with 2 to 8 Alkylene groups, dicyandiamide, an aliphatic dicarboxylic acid or a monoalkyl or dialkyl ester thereof and epichlorohydrin has been produced. 34-. Method according to claim 33, characterized in that the condensation product (3) is one which is obtained from diethylenetriamine, dicyandiamide, adipic acid or a mono- or dialkyl ester thereof containing alkyl radicals having 1 to 6 carbon atoms, and Epichlorohydrin has been produced. 35 «The method according to any one of claims 1 to 26, characterized in that 0.5 to 5 % of the polythiol (1), 0.01 to 0.2 % of the stabilizer (2) and optionally 0.1 to 1 % of the Condensation product (3) »in each case based on the weight of the textile material, ends. 36. The method according to claim 351, characterized in that. the polythiol (1) and the condensation product (3) 409885/1377 used in a weight ratio of (7.5 to 25): 1 . 37 · The method according to any one of claims 1 to 36, characterized characterized in that components (1) to (3) are dissolved in organic solvents or in the form of an aqueous medium by padding or scooping up a temperature between 20 ° and 100 ° C., preferably between 20 and 40 ° C. ■ 38. The method according to any one of claims 1 to 37 »thereby characterized in that the keratin material with components (1) to (3) at a pH within the Ranges from 5 to 12, preferably from 8 to 11, treated. 39 · The method according to any one of claims 1 to 38, characterized characterized in that the impregnated material at temperatures of 80 to 200, preferably from 80 to 160 ° C dries. 40. The method according to claim 1, characterized in that for curing the polythiol, a catalyst in in an amount of 0.1 to 20% by weight, based on the weight of the polythiol. 41. The method according to claim 40, characterized in that the catalyst used is a base, a siccative, sulfur, a sulfur-containing organic compound in which . the sulfur atoms are not exclusively in the form of Mercaptan groups are present, a free radical generating catalyst, a salt of a heavy metal with an acid with an acid strength (-log K) below 5 or a chelate of a heavy metal including the 409885/137 7 Chelates that too. Salts are used. 4-2. Preparation for carrying out the method according to at least any one of claims 1 to 4-1, characterized in that it contains. 1) 0.5 to 5% by weight, based on the weight of the keratin material, Polyth.iol.en has at least two thiol groups per molecule and one molecular weight between 4-00 and 20,000, which are the reaction products of a) polyalcohols, b) alkylene oxides and / or dicarboxylic acids, C-) thiol groups containing carboxylic acids or Cp) Epihalohydrins and Alkalihydx ^ ogensulfiden (these polythiols containing ether and / or ester bonds) or of a ^) polycarboxylic acids, b ^) alkylene oxides or dialcohols and _t C «) thiol group-containing carboxylic acids, 2) 0.01 to 0.2% by weight, based on the weight of the kexatin material, of monomeric stabilizers against the adverse effects of light, and 3) optionally 0.1 to 1% by weight, based on the weight of the keratin material, of condensation products from functional compound or a mixture of two d) dicyandiamide, cyanamide or another bifunctional Connection or one or three of these components, 409885/1377 e) a polyamine containing at least three primary and / or secondary amino groups and ■ £) .an .epihalohydrin. 43. Preparation for carrying out the method according to at least one of claims 1 to 41 ', characterized in that that it contains 1) .- Polythiols with at least two thiol groups per molecule and a molecular weight between 400 and 20,000, which are the reaction products from a) polyalcohols, ■ b) alkyls / oxides and ο ,,) carboxylic acids containing thiol groups or Cp) Epihalogenhydrineη and alkali hydrogen sulfides acts,. 2) Stabilizers against the adverse effects of light and, where appropriate 3) condensation products of ; -. d) dicyandiamide, cyanamide or another bifunctional :; functional compounds that condense with a polyamine can, or a mixture of two or three of these compounds, ■ "..." .. e) at least three primary and / or secondary Amino group-containing polyamine and f) a spihalohydrin. . Preparation according to claim 43, characterized in that that it contains - 409 88 5/137 7 1) Polythiols of the general formula [O-alkylene) OHl _Λ [R]. m ql [O-alkylene) wherein m is at least 1 and in each of the -O-alkylene chains same . or has different values, w 1 or 2, ρ at least 2, (p + q) an integer of to 7, each alkylene group has a chain at least two and at most six carbon atoms between successive oxygen atoms contains, R an aliphatic radical with at least two carbon atoms and X one at least one Thiol group and containing 1 to 18 carbon atoms mean aliphatic radical, 2) Stabilizers of the general formula 2'm I I wherein B ^ and B _{2 are} alkyl or alkoxy with 1 to 8 carbon atoms, Xy, alkylene with 1 to 7 carbon atoms, -CO-, -S- or -0-, I and Y ^{1 are} each hydrogen, hydroxyl or carboxyl, with the proviso that ".at least one hydroxyl is present in the molecule, and m ¹ and m" represent integers from 1 to 4. 4-5. A preparation according to claim 44, ·, characterized in that it contains 409885/1377 1) Polythiols of the general formula ■ L0-alkylene ") _m 0Hl _q-1 [R] [O-alkylene) _m O (CO) _w-1 Xi _p wherein m is at least 1 and each of -O-alkylene chains has the same * or different values, w 1 or 2 ,. ρ at least 2, (p + q) an integer of 3 to 7, each alkylene group has a chain contains at least 2 and at most 6 carbon atoms between successive oxygen atoms, E is an aliphatic radical with at least 2 carbon atoms and X is at least one thiol group and denote an aliphatic radical containing 1 to 18 carbon atoms, and 2) Stabilizers of the general formula wherein B, and B- alkyl or alkoxy with 1 to 8 carbon atoms, X. alkylene with 1 to 4 carbon atoms, -CO-, -S- = - or -0-, Y and Y ¹ each hydrogen, hydroxyl or carboxyl, with provided that at least one hydroxyl is present in the molecule, and m ¹ and m "mean integers from 1 to 4 b ', 3) condensation products of d) dicyandiamide, cyanamide or another 40988 5/137 7 \O bifunctional compound or a mixture of two or three of these components, e ¹ ) one. Polyalkylenepolyamine which, in addition to at least two primary amino groups, also contains at least one secondary amino group, and f) an epihalohydrine. 46. Preparation according to claim 42, characterized in that that it contains 1) Polythiols of the general formulas CH ₀ - (OC ₃ H.) OCOCH ₀ SH CH - (OC ₀ H.) OCOCIl ₀ SH CH ₂ - (OC ₃ H ₆ ) _m 0C OCH ₂ SH OH. CH ₂ (OC ₃ H ₆ ) _m OCH ₂ CHCH ₂ SH OH jH ₆ ) _m OCH ₂ CHCH ₂ SH I OH CH ₂ (OC ₃ H ₆ ) _m OCH ₂ CHCH ₂ SH •and 2) 1,1-bis (3-tert-butyl-4 ~ hydroxy-6-methylphenyl) butane, 1,1,1-TrIs- (3-tert-butyl - ^ - hydroxy-o-methylphenyl) butane or 1,1-bis (5-tert-butyl-4-hydroxyphenyl) butane as' stabilizers. 47. The method according to any one of claims 1 to 41, characterized 409885/1377 characterized in that the keratin material
is made shrink-proof or non-iron. 48. Keratin material, characterized in that it is after
has been treated with the method according to one of claims 1 to 41, 49. Keratin material according to claim 48, characterized in that that it is wool or woolen fabric. 50. Keratin material according to claim 49, characterized in that it is a material which consists of practically 100% keratin fibers. 51. Keratin material according to claim 49, characterized in that it is a material which
Contains at least 30% by weight of keratin fibers. 409885/1377