DE2343620A1 - METHOD FOR SURFACE TREATMENT OF TEXTILES AND FIBERS AND THE PRODUCTS THEREOF - Google Patents

Description

CIBA-GEIGY AG, Basel (Switzerland)

I.W.S. Nominee Company Limited, London (England) 2343620

Case 1-8377 / ARL 194 / +
Germany

Process for the surface treatment of textiles and fibers and the products obtained from them

The invention relates to a method for the surface treatment or modification of textiles and fibers from one keratin-like or keratin-containing material.

Methods with the help of which it is possible to make keratin-like materials shrink-resistant are known; some of them consist of applying a resin to the material in the fabric or fiber form. By Methods for making it shrink resistant are the dimensions

409812/1115

against the keratinous materials by felting Stabilized shrinkage. There are also already known methods with the help of which it is possible to produce keratinous Non-iron materials and many of them use resins that are the same or similar to those as used in the process of making shrinkage resistant be used. This process stabilizes the shape and surface smoothness of the material it prevents deformation when it comes into contact with water. In some procedures, the keratinous material is used in brought to the desired shape before the resin is applied and curing is effected while the material is being applied is held in the desired shape; in other processes the resin is applied and cured after it has been given the desired shape. Processes to achieve the desired shape or form are on known and this includes the use of setting agents, such as water vapor, reducing agents and bases.

A desirable feature of the shrink-resistant processes and ironing relief is that the keratinous to be treated Material should be washable by customary washing methods, especially in household washing machines. To with To be machine washable, the finish on the treated material should be warm against strong movement or hot water containing detergents or detergents, and this condition is severe Test for the treatments.

Among the different classes of resins used for treatment Already proposed by wool are carboxyl-containing poly (butadienes) in which the carboxyl groups by converting the mercapto groups of thioglycolic acid on the ethylene double bonds of poly (butadiene) have been introduced. Such poly-

4 0 9 8 1 2 / -1 1 1 5

(butadiene) proposed in which the number of carboxyl groups per average molecule of the polymer due to the coupling of a few ethylenic double bonds and carboxyl-containing polymers by reaction with lower dimercaptans, such as ethylene glycol-bis-thioglycolate) has been increased. However, these carboxyl-containing poly (butadienes) have an adverse effect because of their adverse effect on the feel or the handle of the material and because of the strict requirements that now apply to shrink resistance and non-iron effects apply and could not be achieved using these substances, but not a general one found commercial recognition. ·

It has now been found that certain substances with two or more äthylenisohen double bonds, which may optionally contain free carboxyl groups, are used can be used to meet these requirements without giving the material an unattractive feel, whereby these polyenes in connection with a specific class of substances used which have two or more mercaptan groups.

The subject of the invention is a method for surface treatment or modification of keratin-like or horny material, in particular of keratin-like or horny Fiber material, in order to give it, for example, non-iron properties or to impart a resistance to shrinkage on washing, which is characterized by that he

1.) the material with a polyene with at least two ethylenic double bonds each in ß-position to one Treats oxygen, nitrogen or sulfur atom per average molecule,

2.) the polyene on the material by reaction with a polymercaptan, which per average molecule min-

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has at least two mercaptan groups, hardens, in addition:

a) the sum of its mercaptan groups and the ethylene groups Double bonds in the polyene is more than 4, preferably 5 "to 8",

b) this in the molecule (i) either the remainder of a polyhydroxy alcohol after the removal of its alcoholic hydro groups or the polyacyl radical of a polycarboxylic acid contains, (ii) contains at least two chains in the molecule, either the residue of a dihydroxy alcohol after the removal of its two hydroxyl groups or contain the diacyl residue of a dicarboxylic acid and via ether or ester oxygen atoms are bound to such a radical, (iii) either an acyl radical of an aliphatic kercaptan carboxylic acid or a residue of an aliphatic iercaptan alcohol contained after the removal of a hydroxyl group in the molecule, which via ether or ester oxygen ^ atone is bound to the best of a dihydroxy alcohol or a dicarboxylic acid,

the total weight of polyene and polymercaptan being 0.5 "to 15% by weight of the treated keratinous material amounts to.

The invention also relates to a keratin-like (horny) material which contains 0.5 to 15% by weight of a product which consists of a polyene hardened with a polymercaptan.

The äthylenisohen double bonds in the polyenes used can each be in ß-position to the same or a different one Oxygen, nitrogen or sulfur atom. The molecular weight of the polyene is preferably within in the range from 250 to 10,000 and particularly preferred

409812 / 11.15

Polyenes are those with at least two ethylenic double bonds, each in a ~ position to a carbonyloxy group stand, especially those from iOrmel

R - (O-alkylene) - O- (CHpCHGHpO), - R ²

where mean:

a is the number 0 or such a positive integer that the average molecular weight does not exceed V / ert 10,000,

b the number 0 or 1,

c is an integer of at least 1, preferably the Number 2 or 3,

R den after the removal of c OH groups from one Compound with at least c alcoholic or phenolic hydroxyl groups remaining or the after removing c OH groups from a compound with at least c COOH groups remaining acyl radical,

Alkylene is any group that has a chain of at least has two and at most six carbon atoms between successive oxygen atoms,

R ^{1 is} a group of the formula -OH or -OOCR ⁵ ,

R -H, an acyl group or the residue remaining after removing an OH group from an alcohol,

with the hatred that R and R are not both acyl mean, if a and b both mean the number O,

2
and R is not -H when b = 1, and

R -H or an iaonovalent hydrocarbon group, can carry the carboxyl or alkoxycarbonyl substituents,

with a total of at least two ethylenic bonds in (x-position to the carbonyloxy groups in the group R and / or in the c groups R and / or in the bc groups R, if present.

The alkylene units in the individual poly (oxyalkylene) chains can be identical to or different from one another and they can be substituted, for example, by phenyl or chlorine groups be. These are preferably -C "H ^ - or -C-zHg

Particularly preferred are polyenes of Porinel I in which R denotes Monoacyl radical of a saturated or ethylenically unsaturated mono- or dicarboxylic acid means, and. in particular those,

ρ
in which R means a group of · Forrael

- CC = CHR ⁵ II

wherein R ^ -H, -Cl, -Br or -C ^ -alkyl and

R ^ mean -H, -CCOH or a group of Forrael

-C-0- (CH ₂ CHCH ₂ O) _b - R ⁶ III R ¹

in which R and b have the meanings given above and R -Π, an alkyl, aryl, aralkyl or alkenyl carbon

'' StoffgruOpe or an aliphatically ^, aromatic or arali-

; f

phasic acyl group means so that the group
Contains more than 24 carbon atoms.

not

R preferably denotes a group which contains 2 to 16 carbon atoms, and carries either a -COOH group or an alkoxycarbonyl group with 1 to 13 carbon atoms, and V? means in particular -CH = CHCOOH or -CH ₂ CH ₂ COOH,
while R preferably denotes an aliphatic radical with up to 60 carbon atoms, in particular a saturated hydrocarbon radical with up to 6 carbon atoms »
when R denotes the radical of a polyhydroxyphenol, it is preferably one of the following formulas

IV

VI

where mean:

VII

Λ 0 9 8 1 2/1 1 1 S BAÖ O & QtNAfc.

Ir -H, -Cl, -Br or an alkyl or alkenyl group with 1 to 9 carbon atoms,

ο ·

R is a carbon-carbon bond, an alkylene hydrocarbon group with 1 to 4 carbon. atoms or an ether oxygen atom and

u is an integer from 1 to 4.

Compounds of the formula I in which R denotes after the removal of c OH groups from an alcohol with at least c alcoholic Hydroxy groups remaining radical or, if a is at least the number 1, after the removal of c OH groups of a carboxylic acid with at least c carboxylic acid groups remaining acyl radical or the after the removal of c OH groups from a phenol with at least c phenolic hydroxyl groups remaining "means can by esterification of the alcohol of the formula

R -

(O-alkylene) OH VIII

2 prepared with a carboxylic acid of the formula HOR or its anhydride or acid chloride if b = 0, while those where b = 1, by conversion of the alcohol of the formula VIII in its glycidyl ether of the formula

- (O-alkylene) _a OCH ₂ CH

• and subsequent opening of the specified epoxy ring by reaction with
can be.

Reaction made with the carboxylic acid of the formula HOR

12/1115

23A3620

Compounds of the formula I in which R denotes after the removal of c OH groups from a carboxylic acid with at least c Carboxylic acid groups remaining acyl radical and a is the number O can be obtained by esterification of the carboxylic acid Formula E (OH) or its anhydride with an alcohol of the

Formula R OH produced v / earth when b = 0, while those where b = 1, produced by reacting the acid R (OH) with a glycidyl ether or a glycidyl ester can be »

Compounds of the formula I in which R denotes after the removal of c hydroxyl groups from a compound with at least c phenolic hydroxyl groups remaining and a and b each denote the number 0, can by esterification of the phenol of the formula -

R (OH) _c X

with a carboxylic acid of the formula HOR or its anhydride or acid chloride, while those where a = 0 and b = 1, by converting the phenol of the formula X in its glycidyl ether of the formula

R (OCH ₂ CH CH ₂ ) XI

and subsequent opening of the specified epoxy ring

2 by reaction with a carboxylic acid of the formula HOR or can be prepared by reacting the phenol X with the appropriate glycidyl ether or ester.

The polymercaptan preferably has an average molecular weight of 400 to 10,000 and it contains pro Molecule up to 6 mercaptan groups. A class of suitable Polymercaptaneii represent poly (alkylene oxide) esters and

409812 / 111S

-ether of the general formula given below nit terminal mercaptan groups

(O ~ alkylene) _f OH

XO-alkylene) -O (CO) X

v / orin mean:
• alkylene and d the meanings given above,

f is a pos? t5_ve integer that can have different fourths in each of the d and e ~ chains,

e is the number 0 or such a positive integer that (d + e) ^. 6,

g is the number 0 or 1,

R "is the remainder of a polyhydroxy alcohol after removal of (d + e) alcoholic hydroxyl groups, and

X is an aliphatic radical which has at least one llercaptan group contains.

It can thus be the partially or fully esterified Compounds of the formula used v / ground

Alkylene).

(O-alkylene)

: ° ' ^C ° - ^C h ^H 2h ^SH ]

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where r ", alkyl enes, d, e and f have the meanings given above and h is a positive integer from 1 to 24 ·.

Esters of the following formula are particularly preferred

E-

(O-alkylene) _f O-CO-CH ₂ .

SH

wherein alkyl en, R and f have the meanings given above have, j is the number 1 or 2 and k is an integer of 3 to 6 mean

These poly (alkylene oxide) esters with terminal mercaptan groups can easily be prepared by reacting a polyhydroxy alcohol with an alkylene oxide and then reacting Esterification of the hydroxyl groups of the adduct with a mercaptan carboxylic acid. Examples of suitable Polyhydroxy alcohols are ethylene glycol, poly (oxyethylene) glycols, Propylene glycol, poly (oxypropylene) glycols, propane-1,3-diol, Poly (epiehlorhydrine), butane-1,2-, -1,3-, -1,4- and -2,3-diol, poly (tetrahydrofurane), glycerine, 1,1,1-trimethylol-ethane and propane, hexane-1,2,5- and -1,2,6-triol, 3-hydroxymethylpentane-2,4-diol, pentaerythritol, dipentaerythritol, Mannitol, sorbitol and adducts of alkylene oxides with the above-mentioned polyols, ammonia or amines, such as Diethanolamine and 5? Etrakis- (2-hydroxyethyl) ethylenediamine. Examples of suitable alkylene oxides are ethylene oxide, Propylene oxide and, less preferred, the butylene oxides, epichlorohydrin and tetrahydrofuran. If necessary, can the polyhydroxy alcohol is treated with an alkylene oxide, e.g. propylene oxide, and then at the ends (tipped) with a other alkylene oxide, e.g. ethylene oxide, are grounded · Preferred mercaptan carboxylic acids for the esterification are Trioglycic acid and 2- and 3-mercaptopropionic acid.

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The esters of the formula are particularly preferred

CH, CH CH,

(OG H ₀ ) .O-CO-G JI ₀ .SH

CH ₂ CH (CH ₂ ) CH -CH,

XVI

2

wherein f and j have the meanings given above and m means the number 2 or 3.

Most preferred among the polythiol esters are those of the formula

CH

(OC ₂ H,.) - OCOCH ₀ SH

Ο Ό X d.

XVII

in which f has the meanings given above, with a molecular weight within the range from 7 ° 0 to 6000. Such esters are commercially available.

0 9 8 12/1 1 1 5

Ethers of the formula are also suitable

(O-alkylene) _f OH

R-

* (O-alkylene)

¹⁰ - ¹

XVIII

v / orin R, alkylene. d, e and f the abovementioned meaning

ΊΟ
functions, R -OH or ~ (0-alkylene) OH and η is an integer of at least Λ , which can have different values in each of the d chains.

Preferred among these ethers are those which also have the Have formula

R-

(O-alkylene) .OCH ₀ CHGH ₀ SH 1 c-tAc \ a

10

XIX

and "are also preferred those of the formula.

_21n ) _t OCH ₂ CHCH ₂ SH

OH

XX

Alkylene, ■ -

in which R, / k, f, η and m have the meanings given above own.

A'ther of the formula can also be used

R-

wherein R, k, f, η and m have the meanings given above.

40981 2/1115

Ethers of the formula XVIII, in which R ^{10 is} -OH, can be prepared by etherifying the hydro> cy groups of an adduct of an alkylene oxide and a polyhydroxy alcohol with epichlorohydrin and treating the intermediate product with sodium hydrogen sulfide, replacing the chlorine with a sulfhydryl group (cf., for example, the US Patent 3,258,495 and British patents 1,076,725 and 1,144,751), while those of the formula XVIII, A7orin R '- (0-alkylene) _n 0H can be prepared by treatment of the same intermediate product first with an alkylene oxide vind then with ITodium hydrogen sulfide (see British patent specification 1 144 7G1),

Most preferred ethers are those of the formula

- (OG H ₆ ) _f OCH ₂ CHCJI ₂ SH

on

CH - (0C-.H _c:) "0CH _o CECII _o SH

pOX d \ d.

OH

CHp-

OH

wherein f is as defined above, particularly those iither having a molecular weight within the range from 700 to 6000.

The second major class of preferred polymer captans comprises Polyester the average formula

CO (O) YSHJ XXIII / P

where mean:

q and r, which cannot be the same ^ the number 0 or 1, ρ a positive integer of at most 6,

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Z is a divalent organic radical that has one or several of its carbon atoms are connected to the specified -O- or -CO units,

Y is a divalent organic radical which has one or more of its carbon atoms with the specified SH group and the specified -0- or -CO units connected, and

W is an organic radical containing at least one SII group must contain, if ρ = 1, and over one or more its carbon atoms is connected to the specified -0- or -CO units.

The average structures of the preferred esters can in particular by one of the following formulas

CO ~ R ^{1 1} -CO-OR ¹⁵ SH ~] XXIV

R ¹⁵ J-CO-OR ¹² O-CO-R ¹⁶ SH j XXV

^L J s

R ¹ 3 Γ oi- CO-R ¹¹ -CO-OR ¹² -0-L- CO-R ¹⁶ SHJ XXVI

R ^ l coC 0-R ¹ 2-0-CO-R ¹¹ CO-L- 0-R ¹⁵ SH1 XXVII.

¹ Z L Jt. _J s

R ¹ 3. ο JLcO-R ¹¹ -CO-OR ¹² -0-L CO-R ¹¹ COO-R ¹⁵ ShI XXVIII PL. J _t Js

R ¹⁵ I Col- 0-R ¹² ^ -CO-R ¹¹ -CO-IOR ¹² OCO-R ¹⁶ SH Ί XXIX ^L Jt Js

H 4- 0-R ¹ 2-0-CO-R ¹ ^ -CO-I- OR ¹² OH XXX

HSR ¹⁶ -C0-0-R ¹² -0-C-C0R ¹⁴ C00R ¹² 0 COR ¹⁶ SH XXXl

· T

and in particular can be represented by one of the following formulas

• 409812 / 111S -

OCO-R ¹¹ -CO-OC H ₀ SHl · XXXII

in dsm I

R ¹ ^ T CO-OR ¹ ^ 0-CO-CH ₀ -SH] 'XXXIII

R ¹ 5l 0 4-CO-R ¹¹ ^ OOR ¹² -oil CO-CH ₀ .SHj XXXIV

L. Jt ³ ^ Js

R ¹ ? F Ο'-Γ- CO-R ¹¹ -CO-OR ¹² -oj- CO-R ¹¹ COOC H ₂ . Sh] XXXV LL- Jt " ^{m 2} ^ Js

- R ¹ ? E CO -) - 0-R ¹² -0-C0-R ¹¹ -C04-0C H ₀ SI τ ι Μ- m «fm

R ¹ ? £ CO-to-R ¹² -0-CO-R ¹¹ -C04-0-R ¹² -0-CO-C .H ₀ .SH

LL Jt a «ij

XXXVI

XXXVII HIOR ¹ ^ 0-CO-CHoOHCO I- OR ¹² OH XXXVIII

I «·

Sl

HS-CH _0. -CO-OR ¹² -0

CO-CH ₀ CHCO-OR ¹² OL-CO-CH ₀ ' SH

SH ^J t

• ~ SH ~ t

XXXIX

where mean:

ä and m have the meanings given above,

R is the remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after the removal of the both -COOH groups,

R is the remainder of an aliphatic, araliphatic or cycloaliphatic diol after removal of the two Hydroxyl groups,

R ^ is an organic radical which contains at least two carbon atoms and is directly connected to the specified ester chains with terminal mercaptan groups via its carbon atoms,

A 098 1 2/1 1 15

14th
R is the remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid with a mercaptan group after the COOH groups have been removed,

t an integer of at least 1, s an integer of at least 2,

R - ^ SH the remainder of a monomercaptan monohydroxy alcohol the removal of an alcoholic hydroxyl group and

R -SH the remainder of a Honomercaptarimonocarbonsäure after the removal of a carboxyl group.

R preferably denotes (a) a saturated aliphatic carbon 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, which can be ethylenically unsaturated, or (c) a mononuclear arylene carbon group with 6 up to 12 carbon atoms.

1?
R can be a saturated aliphatic hydrocarbon chain with 2 to 2 ^ 0 carbon atoms, which can be substituted by methyl groups and SH groups and interrupted by ether oxygen atoms and carbonyloxy groups.

R * can then if it is linked directly to an -O unit is a saturated aliphatic hydrocarbon chain with 2 to 250 carbon atoms, represented by methyl groups and SH groups and substituted by ether oxygen atoms and can be interrupted by carbonyloxy groups, and then, when it is bonded directly to a -CO unit, (a) a saturated aliphatic hydrocarbon group with 2 to carbon atoms which can carry an SH group, (b) a cycloaliphatic-aliphatic hydrocarbon group with

409812/1 116

5 to 51 carbon atoms that are ethylenically unsaturated or (c) is a mononuclear arylene hydrocarbon group having 6 to 12 carbon atoms.

It will be understood that Formulas XXIV through XXXIX represent the average structure of the esters. Because of the incomplete Other substances may also be present in esterification. The polyesters can be made by going in any desired Order with each other

(a) a monomercaptan monocarboxylic acid or a monomercaptan monohydroxy alcohol,

(b) a compound which contains 2 but not more than 2 alcoholic hydroxyl groups, and

(c) a compound containing at least 3 carboxylic acid groups.

If desired, components (b) and (c) can be reacted with one another to form a terminal ester Hydroxy or carboxyl group, which is then esterified with (a). These esters can also be those made can be by esterifying

(d) a Monomercaptanedicarboxylic acid with

(e) a compound that is at least 2 but not more than Contains 6 alcoholic hydroxyl groups, and optionally

(f) a dicarboxylic acid that does not contain any llercaptan group, or an anhydride of such an acid or

(g) a monocarboxylic acid, preferably a monoinercaptan monocarboxylic acid, or

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

It is also possible to use esters which can be prepared by reacting with one another in any desired order
(a) a Monomercaptan monocarboxylic acid or a Monomercaptan

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monohydroxy alcohol1,

(i) a compound that has at least 5 alcoholic hydroxyl groups per molecule contains, and

(j) a compound which has 2 but not more than 2 carboxylic acid groups per molecule contains »

As known to those skilled in the art of making polyesters, a carboxylic acid anhydride can be substituted of the corresponding carboxylic acid can be used, while an alcohol can be replaced by a 1,2-epoxide, wherein an epoxy group corresponds to a primary and a secondary alcoholic hydroxyl group. Examples of substances which contain at least 2 carboxylic acid groups, or their anhydrides, which are used as component (c), (f) or (ö) are succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, sebacic acid, malic acid, citric acid, Tricarballylic acid, pyromellitic acid and dinerized and trimerized, ethylenically unsaturated fatty acids as well their anhydrides (if they exist). The ethylenically unsaturated dicarboxylic acids can be used however, they are not preferred.

In the case of component (a). Monomercaptan monocarboxylic acids used are preferably thioglycolic acid and 2- and 3-hercaptopropionic acid. The monomericaptan monohydroxy alcohols used as component (a) are preferably 2-mercaptoethanol, 1-mercaptopropan-2-ol and 2-mercaptopropan-1-ol. The monomercaptanedicarboxylic acid (d) is preferably Hercaptosuccinic acid (HOOCCH ₂ Ch (SH) COOH).

Among the substances that have at least two alcoholic hydroxyl groups have (b, ^ e, i) include those who already have above as suitable polyhydroxy alcohols for the preparation of Compounds of formula XIV have been enumerated. To the

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Mono-1,2-epo2cyden that used instead of a dihydroxy alcohol v can ground / include those which have been enumerated above, and the glycidyl ethers of alcohols or of phenols, 'N-Glycidy! Compounds and Glycidylestex ¹ of carboxylic acids. Instead of trihydroxy and higher alcohols, honoepoxy monohydroxy alcohols, v / ie glycidol, or a diepoxide, such as a diglycidyl ether of an alcohol or a phenol, can be used *

It is often expedient to use a monofunctional compound such as a monocarboxylic acid (g) or a honohydroxy alcohol (h) as a chain terminator in the preparation of a polymercaptan ester for the use according to the invention, and it is particularly advantageous to use a compound which has a Contains mercaptan group, such as monomercaptan monocarboxylic acids and monomercaptan monohydroxy alcohols, in particular thioglycolic acid, 2-mercaptopropionic acid, 2-mercaptoethanol and 2-Mex * captopropan ~ 1-ol. The polymercaptan esters are generally known substances (see, for example, US Patents 2,455,314, 2,461,920, 2,914-585 and 3,138,573, French Patent 1,503,633 and British Patent 94-1,829 ) Si © can be prepared by joint heating of the reactants in the presence of a catalyst, for example a strong acid (especially an anion exchange resin, of toluene-p-sulfonic acid or ^ O ^ iger sulfuric acid) and an inert solvent such as toluene , Xylene, trichlorethylene or perchlorethylene, the water formed during the reaction can be removed in the form of an azeotrope.

Hach the inventive method fibers or Garments are manufactured that have their original dimensions and their original dimensions when washed in a washing machine keep original shape. The treated material

409812/1115

also exhibits good wrinkle recovery which is an essential Characteristic "in the case of fabrics used to manufacture trousers" is for those in the knee area and on the The back of the knee has a strong tendency to wrinkle. Of course, the crease resistance is also a important advantage for many other items of clothing. Those for inhibiting or preventing entanglement shrinkage inhibit used polyenes and polymer aptanes or also prevent relaxation shrinkage, which is a major problem in knitted goods.

The expression "keratin-like or keratin-containing (horny) material" as used here includes all forms of keratin-like fibers or fabrics and articles of clothing made therefrom, such as fleece, lace, V / ollvorgespinste, noils, yarns, threads, velvets, non-woven fabrics , _; woven fabrics and knitwear, to understand. In most cases, although it is possible and may be advantageous in certain circumstances, the fabrics or the garments made from them are treated, for example to make the fibers in the form of tips shrink-resistant. The material to be treated can either consist entirely of keratin-like fibers or of mixtures of these with synthetic fibers and thread materials, such as polyamides, polyesters and poly (acrylonitrile) and with cellulose materials including the regenerated cellulose materials. In general, however, the material should contain at least 3% by weight of the keratin-like fibers and better results are generally achieved with a material containing essentially 100% keratin-like fibers. The keratin-like (keratin-containing) material can be new or reclaimed material. Preferably, but not necessarily, it is sheep's wool, but it can also, for example, from alpaca, cashmere, mohair, vicuna, guanaco, camel and

409812/1115

Llama hair or mixtures thereof with sheep's wool. In the sail, the keratin-like material is treated simultaneously with the polyene and your polymercaptan, however, it is still within the scope of the present invention if the material goes first in any order the polyene and then treated with the polymercaptan.

Many of those useful in the method of the invention Polyenes and polymercaptans are insoluble in water, but they can be in the form of aqueous dispersions or emulsions be applied. They can also be in the form of Solutions in organic solvents such as alcohols, lower ketones, toluene and halogenated hydrocarbon solvents, in particular chlorinated and / or fluorinated hydrocarbons, such as dry cleaning solvents, Carbon tetrachloride, trichlorethylene and perchlorethylene, upset.

Aqueous emulsions, the convenient carriers for applying the Represent polyenes and polymercaptans may contain (i) a polyene and a polymercaptan, as indicated above, and optionally (ii) an emulsifier and / or

(iii) a protective colloid such as sodium carboxymethyl cellulose, hydroxyether hemicellulose or methyl vinyl ether homopolymers and mixed polymers with, for example, maleic anhydride. The quantities of polyene and polymercaptan used depend on the desired effect. To stabilize knitted fabrics, Λ to 10 ^c / o are usually required, a high degree of shrinkage resistance, retention of the crease-setting and considerable resistance to crease formation can generally be used in woven fabrics with significantly lower amounts of, for example, up to 5 ° / o can be achieved. If, however, the keratin-containing material is loose or loosely assembled fiber material, the amount of products to be applied should be such that it is too

409812/1115

there is no formation of connected fabrics (non-wovens). The handle of the treated material depends of course on the amounts used and also on the relative proportions of polyene to polymercaptan now and then by a simple experiment the optimal amounts can easily be determined.

The desired effects are only fully achieved when the polyene has practically hardened. Curing '(curing takes place under acidic, neutral or alkaline conditions, ^Ζ11Ώ = - * usually at pH 3 to 10. It is often advisable to add a catalyst, and this catalyst is usually added at the same time as the polyene and the polymercaptan applied v / ground, although it can also be applied to the material before or afterwards. The amount of catalyst can vary within wide limits, it is generally 0.1 to 20% by weight, based on the total weight of used polyene and polymercaptan.

Substances that turned out to be useful catalysts are e.g. organic or inorganic Brönsted bases and catalysts producing acids and free radicals. The latter are generally applicable and belong to them organic and inorganic peroxides and persalts, such as benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, Di-isopropyl peroxydicarbonate and ammonium persulfate. As polyenes which have no ethylenic double bonds in the α-position to the carbonyloxy groups can also Brönsted acids can be used. Examples of suitable such acids are sulfuric acid, phosphoric acid and Hydrochloric acid, as well as aromatic sulfonic acids, such as Qoluene-p-sulfonic acid. As preferred polyenes, i.e., those with ethylenic double bonds in the α-position to the carbonyloxy groups, Bronsted bases can be used.

409812/1115 BAB ORIGINAL

Examples of such bases are primary, secondary and tertiary amines, such as triethylaniine and H-benzyldimethylamine, and especially alkanolamines, e.g., mono-, di- and triethanolamine, as well as Alkylenepolyamines, such as ethylenediamine, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, propane-1,2 ~ diamine, Prqpan-1,3-diamine and hexamethylenediamine, as well quaternary ammonium hydroxides, such as tetramethyl ammonium hydroxide, inorganic hydroxides (especially sodium hydroxide) and inorganic, alkaline salts, such as trisodium phosphate, I sodium carbonate, I sodium bicarbonate, I sodium pyrophosphate and ITodium acetate.

Curing is promoted by heating and, if particularly rapid results are desired, temperatures within the range from 35 to 180 ^° C. can be used. The polyene, polymer mercaptan and catalyst, if used, can be applied to the keratinous material in a conventional manner. For example, woolen lace or woolen fabrics can be impregnated by padding or by immersion in a bath, while when clothes or garments are to be treated, it is expedient to spray them with solutions or dispersions of the polyene and the polymercaptan, and even more convenient it is to circulate them in such solutions or dispersions; a dry cleaning machine is particularly advantageous for the method mentioned last.

The polymercaptan and the polyene can also be applied to keratin-like or keratin-containing fibers by scooping out an aqueous medium. As used herein, the term "utilization" refers to the treatment of the fibers with an aqueous solution or emulsion of the polyene and the polymercaptan, odex separated in ⁿ mixture, has been deposited on the parsers are to a large proportion of the polyene and the polymercaptan. Such treatment can be done before, at the same time with

409812/1 1 15

or after dyeing with any anionic dye that is absorbed onto the wool. The exhaustion can be carried out at a pH value within the range from 2 to 10, in particular from ¹ V to 8, and at a temperature from room temperature (for example 20 ^° C.) to 100 ^° C., but generally not above 50 ^° C. v / ground and it usually takes 1 to 2 hours to complete. When a shrink-resisting treatment is required, it is generally more convenient to apply the polyene and polymercaptan to the fabric, although, as indicated above, they can be applied to lace and also to sliver or yarn.

The fabric can be "flat-set" before or after the treatment with the polyene and the polymer aptane and in this way the fabric, in addition to the fact that it essentially retains its original dimensions, also contributes to its flat, smooth appearance during wear and after washing. Of course this can be done with certain types of clothes ironing may not be necessary or even not desired. Ironing is usually done in done in the way that one can use the fabric. Steam under pressure or under atmospheric pressure in the presence a smoothing agent (setting agent) and moisture treated, while the fabric (cloth) is in the flat state; it can also be achieved by having a Applying reducing agent and a swelling agent and the tissue while washing off the excess reagents in the keeps flat state. Another method is the material impregnated with a swelling agent (e.g. urea) and an alkanolamine carbonate (e.g. diethanolamine carbonate), dried and then subjected to a semi-decoding. Desired In any case, the fabric can also be permanently deformed (stiffened) in the presence of the polyene and the polymercaptan, thereby the deformation and anti-shrinkage treatments

40981 2/1 1 1 S BAD ORlQJNAt

at the same time ". Y / enn a permanent smoothing effect (Freedom from ironing) is required, this can be achieved in a wide variety of ways. One Method is to match the material with the polyene and the To treat Polynercaptan, to process the material into clothes or garments and. under verv / endving of Reducing agents, bases or superheated Y / asserdajnpf as Deforming means to introduce folds, v / whether the hardening is carried out before or after the introduction of the folds. A preferred method is to use the finished garment, in which the desired folds have already been created, with the polyene and the polymercaptan, dissolved in one organic solvent, treat; at dies03? method it is better to take this in the form of a solution in an organic Apply solvent because treatment with an aqueous composition leads to a removal of the already in wrinkles formed in the tissue. Another method of creating permanent folds is to use the fabric the polyene and the polymer apt to treat in the area in which a crease is to be created to create the crease and hold the tissue in that position while. Y / arne and pressure are applied.

A method of smoothing and smoothing out keratinous ones Fabrics consists in treating the fabric with a smoothing agent (deforming agent) and making it smooth to make by treating the fabric, while it is still wet, with the polyene and the polymer aptane in the form of an aqueous Medium or in the form of aqueous media, the fabric dries and the polyene by means of the polymer aptane hardens. Finally, the fabric is made into clothes, and if desired folds are introduced into the clothes may be treated with steam in the presence of a setting agent such as monoethanolamine sesquisulfite.

409812/1 116

BAö'ÖRlälNAL

Fabrics, especially knitted woolen goods, can be treated by putting them in a drum that has a Dry cleaning solvent with the polyene and the poly mercaptan and contains a controlled amount of water.

The polyenes and polymercaptans used in the process of the invention can be used in conjunction with anti-pollution. Antistatic, bacteriostatic, anti-rot, flame-resistant egg acheiids and wetting ^ -, water-repellent agents (\? Ie paraffin / ax) and fluorescent brighteners can be used. If the shrinkage resistance or the non-iron effect decreases with prolonged exposure to light on the treated keratin-like material, which can happen, especially if the polyene and / or the polymercaptan contains poly (oxyalkylene) chains, it is advisable to use a stabilizer against the disadvantageous Effect of light ". Suitable stabilizers include compounds with at least one phenolic hydroxy group and at least one alkyl or alkoxy group with 1 to 8 carbon atoms in the same benzene ring, especially compounds with 1 to ¹ V benzene rings, of which at least one has a phenolic hydroxy group in orthor position to such an alkyl or alkoxy group.Specific examples of suitable stabilizers are 1,1 ~ bis-0,5-di-tert-butyl-2-hydroxyphenyl) butane, 1,1-bis-3- (bert. -butyl- ^/ 4 ~ hydroxyphenyl) butane, bis ~ 3- (bert-butyl-2-hydroxy-5-ethylphenyl) methane, 1,1-bis- (2-tert-butyl-4-hydroxy ~ 6 -methylphenyl) butane, Until - ^ - tert. butyl-4-hydroxy-5-methylphenyl) sulphide, octadecyl ~ 3 ~ (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3j 5-di-tert-butyl- 4-hydroxyphenyl) propionate] and the nickel complex of the formula

HO _ // \> -CH ₂ POCH ₂ CH

σ (

40981 2/1115

As a rule, about 0.1 to 5% by weight of the stabilizer based on the weight of the poly (oxyalkylene) containing Polyene and / or polymer aptans.

The following examples are intended to illustrate the invention without, however, restricting it thereto. The parts and percentages given therein relate to weight, unless otherwise stated, and the temperatures are given in ^° C. The polyols mentioned in the production of certain polyenes and polymercaptans are the following compounds:

Polyol I = a glycerine-propylene oxide adduct with an average Molecular weight of 4000; Polyol II, Polyol III, Polyol IV, Polyol V and Polyol XIII = corresponding adducts with an average molecular weight from 4800, 700, J000, 600 and 1000, respectively; Polyol VI = a glycerine-propylene oxide adduct with a terminal Ethylene oxide (ti £> ped) and an average molecular weight of 5000;

Polyol VII = a hexane-1,2,6-triol-propylene oxide adduct with an average molecular weight of 150; Polyol VIII = a pentaerythritol-propylene oxide adduct with an average molecular weight of 4C00; Polyol IX = a 1,1,1-trimethylolpropane-propylene oxide adduct with an average molecular weight of 4040; Polyol X = a butane-1,4-diol-tetrahydrofuran adduct with an average molecular weight of 1000; Polyol XI = an ethylenediamine-propylene oxide adduct with an average molecular weight of 500; Polyol XII = an adduct similar to Polyol VIII with an average molecular weight of 650; Polyol XIV, Polyol XV, Polyol XVII and Polyol XX = poly (oxypropylene) glycols with average molecular weights of 425, 75Ο, -1000 and 2000;
Polyol XVI, Polyol XVIII and Polyol XIX = poly (oxyethylene) -

40981 2/1 1 1 p

~ 29 -

glycols with average molecular weights of 600, 400 and 300,

Po_lyraercapj; to A. "·

A mixture of 800 g (0.2 g-mol) of the polyol I, 55.2 g (0.6 g-LIol) thioglycolic acid, 5 S toluene-p-suD-fonic acid and 350 ml of toluene was stirred in a nitrogen atmosphere heated to reflux. The water formed during the reaction (10.8 ml, 0.6 g-mol) was removed as an azeotrope with toluene. The mixture was cooled and washed with water and the organic layer was separated. After removal of the solvent under vacuum from the organic layer, 793 g (yield 94 % of theory) of the desired tris (thioglycolate) (polymer aptane A) with a thiol content of 0.59 equivalents / kg remained.

It was one from polyol II, epichlorohydrin and poly (2-hydroxy-3-mercaptopropyl) ether made from sodium hydrogen sulfite (U.S. Patent 3,258,495). It had a thiol content of 0.32 equivalents / kg.

Polymers apt to C! · ·

This was made in the same manner as the Polymercaptan A produced, but this time 0.4 g-ilol thioglycolic acid were used. The Polymercaptan C was therefore the bis (thioglycolate) of the trihydroxypolyol I.

Po 3.ym er cap ib an e_D - L_

These were in a manner similar to the polymercaptan A by complete esterification of the o'e ^ ei-lj-Sen polyols III to XI made with thioglycolic acid. In the case of polythiols G-L, perchlorethylene was used instead of toluene and im In the case of polythiol L, no catalyst was used.

0 9 812/1115

It was the tris- (2-mercaptopropionate) of the polyol I, which is produced in the same way as the polymercaptan A had been established.

A mixture of 1,1,1-trimethylolpropane (26.8 g), tolyoxy propylene glycol with an average molecular weight of 425 (17 ° g) j adipic acid (58.4 g), thioglycolic acid (55 »2 g ), Toluene-p-sulfonic acid (3g) and perchlorethylene (35Ο ml) were heated untex "reflux in a nitrogen atmosphere. The water formed during the reaction (25 ml) was removed as an azeotrope with perchlorethylene. The I.Iachung was cooled and washed with water, the organic layer was separated and the solvent evaporated, leaving the Polynercaptan IT (278.9 g) with an oil content of 1.88 equivalents / kg.

The other esters listed in Table I below were prepared in a similar manner.

+49 9 812/1 115 BATH ORIGINAL

Table I.

Polymer captan

Components

substance

O glycerin

Adipic acid butane-1,4-diol Thioglycolic acid thiol content

Molar ratio (A'q / kg) ratio

1 4 4 3

2.35

trimerized linoleic acid *

Polyol XIV thioglycolic acid

T hexane ~ 1,2,6-trio1

dinerized linoleic acid ** • Hexane-1,6-diol thioglycolic acid 3 3

4 2.5

1.09

Q Polyol IV
Mercaptosuccinic acid
n-pentanol 1.
3
3 0.83 R. Polyol IV
Adipic acid
2 - !. lercaptoethanol 1
3
3 0.62 S. Polyol XVII
Mercaptosuccinic acid
Thioglycolic acid 3
2
2 1.15

0.94

U trimerized linoleic acid butane-1,4-diol Thioglycolic acid

3 3

1.64

V polyol III adipic acid butane-1,4-diol thioglycolic acid 1 3 3 3

1.78

W hexane-1,2,6-triol

dimerized linoleic acid polyol XIV thioglycolic acid 1 2 2 3

0.99

40981 2/1115

? '; < J ■ VV f YYY - j V »ί. ij

Continuation from Table I.

Glycerin 1

Adipic acid ·. 2

Polyol XVIII '2

Thioglycolic acid 3

y
Thioglycolic acid

Y 1,1,1-trinethylo! Propane '1

Succinic acid 4 ο RP mixed diprinal alcohols *** 4- '

Thioglycolic acid 3

Z: Triiaerized linoleic acid 1

Butane-1,4-diol 3 2.11

3-Mercapt © propionic acid 3.

A. 1,1,1-Trimethylolpropane 1

Adioic acid 2

Polyol XIV 2 1.95

3-mercaptopropionic acid 3

B ^ j 1,1,1-trimethylolpropane 1

Adipic acid 2 . - .., 2,2-bis- (p-hydroxypropoxy-. ^{Ifc>: 5}

phenyl) propane 2

Thioglycolic acid 3

C ^ ₁ glycerin 1

Adipic acid 4- ^ ₁ - _rv polyol -'XIV '· 4 ^Ί » ^ιυ

Polyol III '1

Adipic acid 3

2,2-bis ~ (p-hydroxypropoxy-1,36

phenyl) propane 3

Thioglycolic acid 3

triilized linoleic acid 1

Polyol XIX 3 _n

Thioglycolic acid. -3

Polyol IV 1

Succinic anhydride "3 0.48

2-mercaptoethanol 3

409812 / 11-18

^G 1 Polyol XII
diraerized linoleic acid
2-mercaptoethanol 1
4th
4th 2343620 ^H 1 Glycerin '
Phthalic anhydride
Butane-1,4-diol
Thioglycic acid e 1
4th
4th
3 ^J 1 Poly oil XX
Mereaptosuccinic acid 11
10 0.40 ^K 1 Polyol XIV
Mercaptosuccinic acid 11
10 1.65 ¹ I. Butane-1,4-diol
Mercaptosuccinic acid 6th
5 3.98 M ₁ mixed diprinal alcohols
Mercaptosuccinic acid
Thioglycolic acid 2
1
2 1.79 H ₁ Polyol XIV
Mercaptosuccinic acid
Adipic acid
acetic acid 11
6th
4th
2 0.93

* The trimerized linoleic acid with an average Molecular weight of about 800 and a carboxyl content of about 3.4 eq / kg was sold by Unilever-Emery N.V., Gouda, Holland under the name "Trimer acid Empol 1043 "received;

** those from the same source under the designation

"Dimer acid Erapol 1022" obtained dimerized linoleic acid had an average molecular weight of about 570 and a carboxyl content of about 3.4 ilqu./kg;

* ♦ * the mixed diprimary alcohols had an average Molecular weight of about 700 and a hydroxyl number of 155 to 165 uncL were by catalytic Hydrogenation of the methyl esters of long-chain aromatic-aliphatic Fatty acids as Diels-Alder adducts of styrene with ethylenically unsaturated acids, such as linoleic acid. The alcohols were sold under the name "Coaerginol 65" by the company Bibby Chemicals Ltd., Liverpool, England.

0 9 812/1115

Polymercaptan O ^

This was done in the same way as the polymercaptan A, but made from polyol V.

Polymercaptan E.

This was the bis (thioglycolate) of polyoli XXIV.

The polyenes used according to the invention were as follows manufactured:

Polyolefin_A__

A mixture of polyol I (200 g), maleic acid reagent (14.7 g) and N-benzyldimethylamine (2 g) was ^{stirred for "100 minutes" at 120 °} C. The polyolefin A obtained as the product essentially had the formula

CH

CH)

(OCH ₀ CH) OE

^a 1

XLI

where a ^ is a number with an average value of 22.3 and E denote the group -CCH = CHCOH.

-δ δ

Polyolefin_B_

536j to 5 g of the as prepared above polyolefin A "was itqu./kg at 120 ⁰ C under Eühren of n-butyl glycidyl ether with an epoxide content of 7.1 (49 g, ie 0.9 nolarer proportion) was added and stirring was 1oc minutes continued at 120 ⁰ C, at which time the epoxide content of the product had fallen to 0. the polyolefin B

40981 2/1115

essentially had the formula XLI, where E -GCH = CHCOCH ₀

Il Il <= -

O O

means, however, it contained OH per average

Molecule 0.1 mol polyolefin Λ.

Polyol £ finJ3_

A mixture of the polyol (1 kg), maleic anhydride (73 g) and triethylamine (10 g) was stirred at 120 ° C. for 90 minutes. Toluene (200 ml), n-butanol (100 ml) and toluene-p-sulfonic acid monohydrate (27 g) were then added to this mixture and the whole was heated under reflux, the water formed being removed azeotropically. After 14 ml of water had been collected, the reflux was stopped and more toluene was added. The solution was washed three times with water / water, dried over magnesium sulfate and filtered and the solvent was removed by evaporation under reduced pressure, the desired What remained was product which essentially had the formula XLI, where E is -CCH = CHCOQ (CH ₂ ^ GH ₅ .

Polyjolef jLn_D_

It was produced in the same way as polyolefin B, but this time 26.5 g (i.e. a 0.5 molar proportion) of the n-butyl glycidyl ether were used. The polyolefin D can be represented by the average formula

r- ^CH 3

... (OGH ₀ CH) ₀ OCOCH = CHCOOh c. ι c. a ^

Ή- 'XLII

CH,

1 5 -η

(OCH ₀ CH) ₀ OCOCH = CiICOOCH ₀ CHGH ₀ O (CH ₀ ) ₇ CH ₇

oh ~ Ί, 5

4098 12/1116 BAD ORiQiNAL

CH

CH

where a, - a number with an average value of 22.3 means.

PolyolefinJS_

The Triglycidyläther from Polyol I (having an epoxy content of 0.58 7i.qu.Ag) (200 g), methacrylic acid (10 g), Triäthylarain (2 g) and hydroquinone (0.2 g) were dissolved for 3 hours at 120 ⁰ C, at which time the epoxy content of the mixture had fallen to 0 v / ar. The polyolefin E essentially had the formula XLI, where E is

«CH

OH

The triglycidyl ether of Polyol III (with an epoxy content of 2.7 Jiqu.Ag) (500 g), methacrylic acid (116 g), triethylamine (6 g) and hydroquinone (0.5 ß) were stirred for 2 hours at 80 ° C and then for 3 hours at 120 ° C, whereby at this point the epoxy content of the mixture had dropped to 0 v / ar. The polyolefin F had essentially the formula

CH

? ^H 3

(0CH ₀ CH),

OE-

XLIII

where a ~ is a number with an average value of 3.5 "wad" E the group

CH, -CH ₀ CHCH ₀ OCC = CH ₀

c. j c. it d.

OH

mean.

Poly £ l, efin_G_

To a stirred solution of the polyol I (200 g) and triethyl

409812/1115 BAO ORiQtNAL

amine (22 g) in dry acetone (200 g) became fresh added distilled acryloyl chloride (20 g). The mixture was stirred at room temperature for one hour and then refluxed for 5 hours. Thereafter it was filtered, p ~ methoxyphenol (0.2 g) was added, to prevent polymerization, and the solvent was evaporated under reduced pressure. The polyolefin G essentially had the formula XLI, where E means

-CCH = CH ₀
0

Polyol £ fin_H_

Acrylic acid (39 g)> triethylamine (2.4 g) and hydroquinone (0.2 g) were stirred together at 80 ° C. while the triglycidyl ether of polyol III (200 g) was added over a period of 75 minutes. The mixture was further stirred for one hour at 80 ⁰ C and then for 3 hours at 120 ⁰ C, at which time the epoxide content of the product had fallen to 0. The polyolefin H had essentially the formula XLIII, where E is

-CH ₀ CHCH ₀ OCCH = CH ₀
OH 0

Po_lyol_efin_I_

The 1,4-butane diol diglycidyl ether with an epoxide content of 7.8 equiv / kg (100 g), 1 g of triethylanine and 0.1 g of hydroquinone were heated to 120 ° C. with stirring and heated over a period of 1 hour 56.2 g of acrylic acid were added. The mixture was v / urther 2 hours at 120 ⁰ C held, after which the epoxide content of the product was the 0th The polyolefin I essentially had the formula

OH 0

XLIV

SAD OBfGINAt.

Butane-1,4-diol (180 g), maleic anhydride (592 g) and Iriathylamine (10 g) were mixed together, whereby the temperature of the mixture rose rapidly to 95 ° C due to an exothermic reaction. After cooling the mixture up 80 C froze, she. Thereafter, an n-butyl glycidyl ether was used with an epoxy content of 7 »1 aqu./kg (500 g) was added and the mixture was heated to 120 ° C for 100 minutes. The polyolefin J obtained as the residue had essentially the formula

0 0 OH

Il

CHpCHpOCCH = OIICOCHpCHGH _p O (GII) _v CH ₇

XLV

Polyolefi.n_K_

Äthylenglykolmonoiiiethyläther (76 g), 93 g of maleic anhydride and J g H-Bensyldinethylamin were for 100 minutes together heated to 120 ⁰ C, then n-butyl glycidyl ether (141 g) was added and heating was v / urther 2 hours at 120 ⁰ C. continued. After the mixture had been cooled to 60 ⁰ C, 98 E maleic anhydride was added and heating at 12O ⁰ C was continued for another 2 hours. The polyolefin IC obtained as the product essentially had the formula

CH ₂ 0CH _o CH _o 0CCH-CHC0CH _o CKCH _o 0 (Cn _o ) ₂ CH _x

3 22 ti Il 2 | d d. $ 5

0 0 OCCH-CKCOE

It Il

0 0 wherein E is hydrogen.

This was prepared by heating 208 g of polyolefin K ait 70 g of n-butyl glycidyl ether ^{to 120 0} C for a period of 100 minutes and it had essentially the formula XLVI, where E means -CH _{2 CHCHpO (CK 2} ^

OH

409812/1116

Pol_yol_ef in_ll_

A butane-1,4-diol digylcidyl ether with an epoxy content of 7.4 eq / kg (108 g), itacoric acid (65 g), n-butyl glycidyl ether (28.1 g), benzyldimethylamine (2 g) and hydroquinone ( 0.2 g) were mixed together and heated to 120 C, wherein the temperature of the mixture rose to 250 ⁰ g at the onset of an exothermic reaction. The product was quickly cooled to 120 ° C. and heated to this temperature for one hour. The polyolefin M essentially had the formula

(CH ₂ ) ₄ 0

H I (CIU) "0 CH ^ CIICIUOCOG CCOCIUCHGIUO H

II

₀ CHGII ₀

OH 0 OH

y y

XLVII

PoJLy £ lefi.n_H_

Glycerin (92 g), succinic anhydride (JOO g) and. lT ~ benzyldimethylamine (4 g) vnirden for 1 hour at 120 ⁰ C heated, then were Glycidylnethacrylat (426 g), IT-benzyldimethylamine (4 g) vjid hydroquinone (0.8 g) were mixed together and over a period of ^> 0 Minutes while maintaining the temperature at 120 ° C. Finally, heating was continued at this temperature for an additional seven and a half minutes. The exclusive polyolefin IT had borrowed the formula in v / es

CH ₂ - OGOGH ₂ CH CH-, 0 _o G00CH _o CHCH _o 0E CH ₂ . • I.
CH -
CH ₀ - —— where E means -CC =
II OH -J d. Polyolefin O

XLVIII
-J 3

Adipic acid (JO g), glycidyl methacrylate (58 »2 g), triethylamine (1 g) and hydroquinone (0.1 g) were added for 2 1/2 hours

09 8 1 * 2 / Λ 1 1 5

heated to 120 0. The polyolefin O obtained as the product essentially had the formula

? 3 COOCH ₀ CHCH ₀ OCc = CH

OH

LI

This was made in the same way as polyolefin O from 570 β "Diner acid Empol 1022" and 284 g glycidyl methacrylate made using 8.5 S triethylamine and 1 g " Hydroquinone and heating for 1 3/4 hours. It basically had the formula

CH ₇ ι 3

-C00CH _o CHCII _o 0CC = CII ₀

d ι £ -ii <~

OH 0

v / orin D denotes the C ₅ ^ H / - _O residue of the dimerized linoleic acid after the removal of both carboxyl groups.

Polyolefin_Q_

This was prepared by heating 116 g of maleic acid, 228 g of allyl glycidyl ether, 36 triethylamine and 0.3 S hydroquinone to 120 ^° C. over a period of 1 1/2 hours; it basically had the formula

Il

OH
ι

ICHCOCH ₀ CHCH ₂ O-CH ₀ Ch = CH

Poly £ lefin_R_

This was prepared by heating 59 g of succinic acid, 114 g of allyl glycidyl ether and 1.73 g of N-benzyldimethylamine to 120 ^° C. for 2 hours and it essentially had the formula

409812/1115

LII

Po3, y_qlefin_S_

The polyol XIII (333 g) ₅ succinic anhydride (100 g) and N-Benzyldiraethylamin (4.3 g) were heated to 120 ⁰ C for 2 hours, at 60 ⁰ C -then cooled while Allylglycidylather (114 g) and N- Benzyldiiaethylamine (1 g) were added and the mixture was ^{heated to 120 °} C. for more than 2 hours. The polyolefin S obtained essentially had the formula

? ^H 2 ~ CH ₅ 0 OH

CH-I - (OCH ₂ CH) _a OCOCH ₂ CH ₂ COCH ₂ CKCh ₂ OCH ₂ CH = CH ₂ "] LIII

IL ^a 3 J,

where a-, a number with an average value of 5.2 means.

Polyolefin_T_

This was prepared in a similar manner from glycerine (92 g), succinic anhydride (300 g) and IT-benzyldimethylanine (4 g) followed by the addition of 342 g of allyl glycidyl ether and 3 g of H-benzyldimethylanine. It essentially had the formula XLVIII, where E is -CH ₂ CH = CH ₂ .

2,2-bis (4-hydroxyphenyl) propane (114 g), n-butyl glycidyl ether (130 g) and N-benzyl-aiain (2 g) were heated for one hour at 120 ° C, then cooled to 7O ⁰ C . Maleic anhydride (98 g) was added and heating was continued at 120 ° C for an additional 100 minutes. The polyolefin U had essentially the formula

409812/1 115

ο -,

OCn ₂ CHOCOCH = CHCOH

CH ₀ O (CH ₀ ), CH _x -J d dot)

LIV

PolyolefinJT_

2,2-bis (4-hydroxyphenyl) propane (114 g) vmrde (e.g. 30.5) with propylene oxide to Bückflußtemperatur (61 ° C). A 40% strength aqueous sodium hydride solution (0.57% ) was added and the reaction was allowed to proceed for 50 minutes, the temperature rising ^{to 66 ° C. during this time.} A further amount of a 40% sodium hydroxide solution (0.57 ß) was added and the mixture was refluxed for a further 2 hours to ensure that the temperature rose to 100 ° C. There were added v / urde propylene oxide (30.5 g) and the refluxing was continued for another 4 hours, maintaining the temperature at 14O ⁰ C increase during this time. The solution v / urde to 100 ⁰ C cooled and there was added maleic anhydride (98 g) and IT Benzyldiinethylamin (2.75 p), and the mixture was heated for 100 minutes at 120 ⁰ C. The polyolefin V obtained essentially had the formula

CH

CH-,
1 3

OCH ₂ CIiOCCK

CHCOH

PolypJLef JLn_W_

A 4 / volume aqueous sodium hydroxide solution (50 ml) was added Cooled 3 ° C. Purfuraldehyde (97 g) and acetone (29 g) were mixed together and slowly added over a period of 1 hour while the temperature was 10 to 16 ° C was held. This temperature was maintained for an additional 1 1/2 hours. After getting the 'mixture overnight had failed, had become a yellow crystalline

09812/1115

_ 43 -

Precipitated solid. This pest was filtered off with dilute acetic acid (2%) and then with distilled water until the pH value is neutral wash and finally dried in a vacuum oven at 35 C, The polyolefin W had essentially the formula

CH = CH - C - CH = CH -,

| Tj | δ ^ J

LVI

Polyolef5.n_X_

This was D.iallylorthophthalate.

Polyolefin_Y_

The polyol XV (300 g), maleic anhydride (32.66 g) and xylene (66.7 c) were stirred together and heated under reflux for one hour (170 ⁰ C). The solution was cooled to 150 ° C., 3 ₅ 33 U of toluene-p-sulfonic acid were added, the mixture was heated under reflux again and the water released during the esterification was removed by azeotropic distillation using a Dean-Stark trap. The mixture was refluxed for 3½ hours collecting 6 ml of water. The solution was cooled to 50 ° C. and neutralized with an aqueous potassium bicarbonate solution, the water and the xylene were removed by distillation and the residue was filtered off. The polyolefin Y essentially had the formula

CH ₃

H-- 0 (CH ₀ CHO) ₀ OCCH = CHCO- d. 3.1,

- 0 ₍₀ CH CHO) H LVII 5 ^{2 a} 4

where a ^ is a number with an average value of 12.6 means.

PolyOlefin_Z_

Polyolefin Z was prepared in a similar manner to polyolefin Y

40981 2/1115

/ I / I _

made from polyolefin XVI (240 g). It basically had the formula

H- _{O (CH 0} CH ₀ O) OCCH = CHCO-O (CII ₀ CH ₀ O) ₀ H LVIII 2 2 a ₅

where a ^ is a number with an average value of 13.2 means.

Polyolefin A _x ,

Butane-1,4-diol (108 g), maleic anhydride (98 g) and xylene (135 ε) were stirred and refluxed for 2 hours heated together «The water formed during the reaction was by azeotxOpe distillation using a Dean Stark trap removed. It became toluene-p-sulfonic acid (2 g) was added and refluxing was continued for an additional 2 hours. The product was, as for that Polyolefin X described, isolated »The resulting polyolefin A ^ j essentially had the formula

HL 0 (CH ₀ ) ^ OOCCH = CHCO-

Polyolefin B ^

The polyolefin B ^ was prepared in a similar manner as the polyolefin S from the polyol V (200 g). It essentially had the formula LIII, where a ^ is a number with an average value of 2.9.

Polyolefin C.

^{The polyol XV (375 g) was heated to 110 °} C. for one hour under a vacuum of 3.5 mm in order to remove water and other low-boiling material. The vacuum was released with nitrogen, toluene diisocyanate (174 g) was added and the mixture was heated to 120 ° C for 4 1/2 hours under nitrogen. After that the solution was up

/.09812/1 1 1 5

80 ° C. and diallylamine (97 δ) was added; an exothermic reaction occurred and the temperature of the mongrel rose to 120 ^° C. The mixture was kept at this temperature for a further hour to complete the reaction. The polyolefin G ^, was an allophanate, which essentially had the formula

C ₇ IL

CH ₇

\ / XX * y j

O (CH ₀ CHO) ₀ OCIJH- / '^ _MHC0HH (CH _o CH = CH _o ) _o

where a, - a number with an average value of means.

Polyolefin D ^

The polyolefin ~ D * was triallyl isocyanurate.

Polyolefin E ₁

The polyol X (255 g) was mixed with dibutyltin dilaurate (0.15 s) and ^{heated to 110 °} C. for one hour under a vacuum of 2.5 ram Hg in order to remove all traces of water. The mixture was then cooled to 60 ° C, the vacuum was released with dry nitrogen gas, and allyl isocyanate (41.5 g) was added dropwise so that the temperature was maintained at 60 ° C. After the addition had ended, the solution was kept at 60 ^° C. for a further 3 hours. The excess allyl isocyanate was removed by heating the product under a vacuum of 3.5 mm Hg for one hour at 110 ° C. The polyolefin E ^ obtained as a residue essentially had the formula

OCNKCH ₂ CH =

7 ^d

LXI

where a «is a number with an average value of 6.3 means* .

12/1118

Polyolefin F ₁

The polyolefin F. was made from a commercially available diisocyanate prepolymer with an isocyanate content of 4.10 % . Dry allyl alcohol (12.9 g) was added to the isocyanate prepolymer (I5I ε). The mixture was stirred for 17 hours at 100 ° C. under nitrogen. The excess allyl alcohol was then removed by heating the mixture for 8 hours under a vacuum of 2.5 mm. Hg removed to 100 ^{° G.}

Polyolefin G ₁

The polyolefin G ₁ was piallylaiaine.

Various wetting agents were used in the following examples used, namely:

Wetting agent I: an adduct of p-lfonylphenol (1 mol) and ethylene oxide (9 col);

Wetting agent II: an adduct of mixed primary, aliphatic C ₁ ^ - and C ₁₈ ~ aliens (1 mol) and xethylene oxide (70 J.iol); Wetting agent III: an adduct of p-octylphenol (1 mole) and ethylene oxide (8 hol);

Wetting Agent IV: Similar to Wetting Agent II, it contained but only 8 mol of ethylene oxide ρι · ο LIoI of the mixed Amines;

Wetting Agent V: the lithium salt of an adduct of p-l-tonylphenol and ethylene oxide (1.5 LIoI), esterified with sulfuric acid.

The methods used in the examples to wash the samples of the treated keratin-like (keratin-containing) material were the following:.

Method: A

With this method, the relaxation and entanglement shrinkages were observed measured separately.

A mixture of 147 S sodium dihydrogen phosphate dihydrate, 200 g disodium hydrogen phosphate and 12.5 U wetting agent I.

0 9 8 12/1115 BADQftlQfNAL,

vnirde diluted to 25 liters in a "Cubex" washing machine with distilled water. This solution was warmed to 40 ° C and then samples of the keratinous material (no more than 50 g) and enough cotton for dietary fiber were added to bring the weight of the batch to 1 kg. The contents of the Cubex washer were rotated for 15 seconds, left for 15 minutes, and rotated for 5 minutes; the samples were dehydrated, ^{rinsed with distilled water at 40 °} C. and spun in a centrifuge dryer. The relaxation shrinkage is the change in % "of the surface area of the samples, calculated from the changes in the linear dimensions.

After that, the samples were put together with enough fresh cotton ballast Returned to the Cubex washer to replenish the load to 1 kg and 147 g of ifetrium dihydrogen phosphate dihydrate were obtained and 200 g of disodium hydrogen phosphate, diluted to 25 1 with distilled water / water, are added. Of the Content - has been changed to JO minutes instead of 5 minutes rotated at 40 C. The entanglement shrinkage is calculated accordingly from the change in the linear dimensions in the relaxed state.

Method B.

This was similar to method A, with the exception that the second wash liquid consisted of 88.2 g of sodium dihydrophosphate dihydrate and 120 g of disodium hydrogen phosphate, diluted to 15 liters with distilled water, and the second wash lasted an hour.

Method * (J

This method is the same as method B, but with the Exception that the second wash lasted 5 hours.

409812/1116

23A3620

Method D

The samples were washed in an electric English reversible washing machine, which had been set to program 5 and time control Kr. 1, at 40 ° C., the washing liquor being an aqueous solution containing 2 g of soap flakes per liter and 0, Contained 8 g of anhydrous sodium carbonate, using a caustic / sample ratio of about 30: 1 (by weight). The samples were rinsed in cold water, spun in the machine, and then dried on full heat in a Parnall tumble dryer for 30 minutes. The samples were then ^{stored for 16 hours at 20 °} C. and 65 % relative humidity. The surface shrinkage (total value of the relaxation and entanglement shrinkage) was also calculated from the linear shrinkage measurements «

According to regulations 7b and 71 ÖLes International Wool Secretariats (IQVS), a woolen fabric washed according to method A or B should have a surface felt shrinkage of less than 5 % . To comply with IY / S regulation 72, the surface relaxation and entanglement shrinkage of the woolen fabric should be less than 8 % when the fabric (fabric) is laundered by method C.

By stirring together using a high-speed stirrer of 50 parts of polyinercaptan, 2.5 parts of wetting agent I, 47.5 parts of water and optionally 0.1 to 0.5 Parts of carboxymethyl cellulose were emulsions of the polymer made captane. The emulsions of the polyolefins were made in a corresponding proportion of 50 parts of polyolefin and 5 parts Wetting agent II, 45 parts by volume and optionally 0.1 up to 0.5 parts of carboxymethyl cellulose.

409812/1 1 16

BeisDiol 1

The fabric or fabric used was a wool flannel weighing about 170 g / m · The pH of its aqueous extract was 7.1. Samples were flannel to a pickup of 300% with a Perchloräthylenlösung (Experiments ITr 1, 2, 11 13 to 17 and 19,.)> Which indicated in the following Table II - containing components, impregnated. The amounts of polythiol, polyene and catalyst are expressed in % of the weight of the flannel sample. The experiments ITr. 3, 5} 7, 9 and 4, 6, β, 10, 12, 18, 20 and 21 were carried out in a similar manner, but this time the components were applied in the form of trichlorethylene solutions or in the form of 50% strength aqueous emulsions became. Then, the samples were stored in a forced air oven for 15 minutes at 65 ⁰ C and dried at room temperature and room humidity.

At intervals of 1 to 22 days after the samples were impregnated, they were washed by method D and dried. The untreated fabric exhibited area shrinkage an average of 22.9%. The bit den The results obtained from treated samples are given in Table II below.

4 0 9 812 UJ 15

Table II

Ver Polyinercaptan Polyolefin Catalyst Oberfläcberischrur.pfuv:

search "(SS) 00 C *

1 - B 3.0 DETA ^ 0.15 19.9

2 -. B 3.0 PPDA ² 1.5 21.7 '

3 A 1.5 A 1.5 DETA 0.06 4.4

4 ⁴ A 1.5 A 1.5 DETA 0.06 5.4-4.5 '4.0

5 N 0.75 A 2.25 DETA 0.06 6.4

6 ⁴ IT 0.75 A 2.25 DSTA 0.06 6.4

7 Q 1.3 A 1.7 DETA 0.06 5.4-

8 ^ Q 1.3 A 1.7 DETA 0.06 6.9

9 S 1.3 A 1.7 DETa 0.06 4.9 5.9

S 1.3 A 1.7 DETA 0.06 6.4

D 1.5 B 1.5 DETA 0.06 6.5 4.9 5.5 4.0

D 0.4 B 3.0 DETA 0.12 6.9 8.8 8.8 7.4

O ₁ '1.0 B 3.0 DETA 0.12 3.5 4.0 4.0 3.5

D 0.6 C 3.0 DETA 0.06 11.7 7.9

D 0.4 D 3.0 DETA 0.24 9.2

D 0.4 E 3.0 DETA 0.12 10.2 6.5 * D 1.7 F 1.3 DETA 0.06 6.5 6.0

D 1.5 P 1.5 DETA 0.12 8.3 8.8

19 'D 1.7 · G 1.3' DETA 0.06 -5.4-4.5 3.5 3.5

D 1.5 G 3.0 DETA 0.12 10.2 9.3

D 1.5 H 1.5 DETA 0.12 9.8 10.2

DETA = diethylenetriamine

PPDA = a poly (co-oxypropylene) diamine with an average Molecular weight of 2000

^ Cured by additional 5- ^E1 i ⁿ ütiges heating to I50 C

hardened by additional 2 1/2-minute steam treatment r.'iait a steam iron

Instead of polymercaptans A, D, N, Q, S and O ^ The esters and polyester C can be used EM ₁ 0, P, R, T-B JXJ and ether.

409.81 27.I.I 1 5 BATH

r 51 -

Example 2

A bath was prepared which contained 60 g of a 0 % strength aqueous emulsion of polythiol A, 60 g of a 5> 0% strength aqueous emulsion of polyolefin A and 880 g of water -Y7ert of about 5) soaked and squeezed out so that the uptake was 70 % , and then it was dried at 120 ° C. for 2 minutes. The fabric, which could then be made into clothes in the usual way, met the provisions for washing machine washability of IWS regulation 71. Similar results were obtained with different absorption times (50 to 120 μm) and when drying among others Conditions (e.g. one minute at 130 ° C or four minutes at 110 ° C), however conveniently at 80 ° C or above, or using only JO g or up to 80 g of each emulsion per kg of bath liquid.

Example 3

Example 2 was repeated using the bath liquid as a catalyst 0.2 to 2 g of anhydrous sodium carbonate, Sodium bicarbonate, disodium hydrogen orthophosphate or honoethanolamine contained, the pH of the liquid depending on the added catalyst up to 10 The results were as good as in Example 2 obtain. However, with ammonia as the catalyst, the shrinkage resistance effect, although pronounced, was not that good.

example A-

As described in Example 2, a bath liquid was prepared, which, however, contained 2 g acetic acid per liter, the pH-7 / ert of the liquid being about 4-. There were other liquids that contain mixtures of mono-

Λ 0 9 8 1 2/1 1 1 p

r 52 -

sodium dihydrogen phosphate and disodium monohydrogen phosphate contained in such amounts that the pH / ert of the various liquids was between 2 and 6. A wool knit fabric, that had been treated with the liquids as in Example 2 "also met the shrink resistance requirements the IV / S regulation 7 ^.

Example 5

A knitted pullover material (50 kg) was impregnated with a liquid containing 25 parts of polythiol A, 25 parts of polyolefin A and 950 parts of perchlorethylene, and the uptake was adjusted to 100% by shaking, centrifuging or wringing out the material. The impregnated material was dried at 80 ° C. for 5 minutes in a stream of warm air. The treated material, which was washed immediately, met the shrink resistance requirements of IWS regulation 7I

Example 6

A wool fabric was soaked up to an absorption of 80 % with a liquid composed of 60 parts of a 50% aqueous emulsion of polythiol-C, 50 parts of a 50% aqueous emulsion of polyolefin A, 5 parts of anhydrous sodium carbonate, 2 parts of wetting agent III "and 883 parts of water. The fabric was ^{dried (hardened) by heating to 160 °} C. for 1 minute, after which it met the requirements of IWS regulation 7I.

Example 7

This example describes the application by scooping up. In a yarn dyeing device, 100 kg of v / o yarn were put on Dyed in the usual way with a real dye, then the yarn was rinsed and soaked in 30000 liters of water at 20 to 30 ° C brought. Add 3 kg of 80% acetic acid and 400 g

4 0 9 8 12/1115

r 53 -.

Wetting agent IY added. The liquid was circulated for 10 minutes and then 4 kg of a 50% strength aqueous emulsion of the polyolefin A and 4 kg of a 50% strength aqueous emulsion of the polythiol Λ were added. The mixture became clear and the agents completely deposited on the wool within 15 minutes. After a further 15 minutes the bath was removed and the wool was squeezed out and dried. Its shrinkage resistance effect met the requirements of IWS regulation 7b.

Example 8

A dyed, 100% wool flue urea was impregnated with a liquid which contained 25 parts of a 70% aqueous solution of monoethanolamine sesquisulfite, 20 parts of ionoethanolamine, 50 parts of urea and 905 parts of water, the absorption being 50 ^c / ° . The fabric was rolled up and treated with saturated steam in an autoclave for 5 minutes at 102 ° C, then it was dried at 90 ° C. Thereafter, the pulp was smoothed in the above mentioned manner (flat set) and to the recording of 60 ° o impregnated / with a liquid having a pH of 6 and composed of 60 parts of a 50% aqueous emulsion of polythiol A , 50 parts of a 50 liters aqueous emulsion of polyolefin A, 1.7 parts of monosodium dihydrogen phosphate, 2.4 parts of dina-trium hydrogen phosphate and 885.9 parts of water. The fabric was dried on a tenter ^{at 120 ° C. for 2 minutes.} Its surface remained smooth and it met the shrinkage resistance requirements of IWS regulation 72.

For smoothing, a liquid could be used in place of the above-described liquid with satisfactory results those used containing only 10 or up to 60 parts of monoethanolamine sesquisulfite or the same amount by weight

40981 2/1115

Matriuimaetabisulfit contained. The monoethanolamine could go away, left v / ground or increased to 30 parts v / ground and the urea could also be omitted or increased to 1CO parts, the amount of water being adjusted accordingly was to reduce the weight of the bath to 1000 parts in each case bring to.

Example 9

A liquid consisting of 60 parts of a 5 ° emulsion of polythiol A, 50 parts of a 50% emulsion of polyolefin B _1, 5 parts of sodium carbonate and 5 & 5 parts of water was applied to a dyed flannel fabric, the uptake being adjusted to 80% and the flannel was heated for 3 minutes at 110 ⁰ C. The flannel fabric met the shrink resistance requirements of IWS regulation 7b.

Example 10

A full fabric was impregnated to an absorption of 7 % egg with a liquid which had a pH value within the range from 4 to 6 and consisted of 50 parts of a 50% aqueous emulsion of polyolefin A, 10 parts of a 50% aqueous emulsion of polythiol D, 2 parts of wetting agent III, 5 parts of sodium dihydrogen phosphate and 933 parts of water. The fabric was dried by 4-iainütiges heating at 110 ⁰ C, stored for 12 hours 5 minutes at 102 ⁰ C deka advantage long and dried by centrifugation for 2 minutes. The fabric treated in this way met the requirements of IWS regulation 7I.

Example 11 .

There was a similar comparable Wollflanellstoff'wie in Example 1

BATH ORIGINAL

applies, but the pH of its aqueous extract was 3.1 and its relaxation shrinkage was 6.3 % treated as described in Example 1. The results obtained are given in Table III below.

Table III

Ver Polymercaptan polyolefin catalyst surface shrinkageOfxmg such (%) (%) (55). (£) Kr. After χ days

A. 2 , 48 I. O , 52 DETA O , 06 5, 1 Q 5, 2 6, 8th 22nd A. 2 , 28 J 0 , 71 - 11 9 4th 23 A. 2 , 73 T / O , 23 DETA O , 06 2 • 7, 24 8th 4th

Instead of the polyolefin I, J or Y /, the polyolefins could also be used K-V uses v / earth.

Example 12

This example illustrates staining and anti-shrinking in one proceeding.

The procedure described in Example 7 was repeated, This time, however, the staining stage was left out until the point in time when the bath liquid was exhausted of the polymercaptan on the wool had become clear. 5OO g of Alizarin Past Blue BE were added to the bath and the Fluid was absorbed over a period of 20 minutes

-O

80 C and held at this temperature for 30 minutes. Then the yarn was rinsed with cold water and dried. The wool, dyed blue, filled them Requirements of the IWS regulation 7ΐ> ·

Ο 9 8 1 2/1115 BAD ORIGINAL

example

In this example a flannel cloth was used which was similar to those used in Example 1, but the aqueous extract of which had the pH word 9.4. The flannel fabric was soaked with a trichlorethylene solution up to an absorption of 100 % until the amounts of polyolefin, polythiol and catalyst indicated in Table IV below remained on the wool. The treated fabrics were dried in a forced air oven at 80 ° C. for 15 minutes at their original dimensions; those containing toluene-p-sulfonic acid or a peroxide catalyst were heated to 145 ° C. for an additional 5 minutes. Then they were washed together with an untreated sample for comparison by method B, and their surface entanglement shrinkage values were determined.

Table IV 1.52 Catalyst (> δ) 0.06 Surfaces-
matting
schruuipfunnjO-j) Polymercaptan (, -δ) Polyolefin {%) '1.37 DETA- 0.06 1.8 S 1.48 Y 2.31 DETA 0.06 2.6 S '1.63 Z 2.19 DSTA 0.06 4.6 O ₁ 0.69 Y 1.24 DSTA 0.1 4.3 O ₁ 0.81 Z 1.24 (BO) ₀ - * 0.5 4.2 O ₁ 1.76 ^A 1 1.76 IP.PDC ^b 0.3 3.7 O ₁ 1.76 1.57 PTSA ⁷ 0.3 2.4 O ₁ 1.27 ^B 1 0.66 PT3A o, 3 0.0 O ₁ 1.43 ^C 1 2.0 PTSA 0.3 1.9 O ₁ 2.34 2.15 PTSA 0.3 2.7 O ₁ 1.0 E ₁ 0.43 FJ) SA 0.3 0.0 O ₁ 0.85 ^P 1 1.96 PTSA 0.3 1.2 O ₁ 2.57 ^G 1 - PTSA - 1.7 O ₁ 1.04 S. - 18.8 not- tehan- -
delt -

409812/1115

( ^B _z O) p ^: benzoyl peroxide

IPPDC: a 20% solution of diisopropyl peroxydicarbonate in isopropanol
PPSA: toluene-p-sulfonic acid. '

In other experiments, the wool flannel fabric used gave an aqueous extract with a pH / ert of 5.5, its relaxation shrinkage was 15.2%. It was impregnated with a trichlorethylene solution up to an absorption of 3 ° 0 % until the amounts of polyolefin, polythiol and catalyst indicated in Table Y below remained on the wool. The treated ITlanell cloth was dried in a forced air oven at 80 ° C for 15 minutes, then heated to 150 ° C for 5 minutes.

The samples were subjected to a relaxation process according to method A and their relaxation shrinkage was determined. After that they were 3 eggs according to method D without to be washed in a drum in between. Finally, the dimensions of the wet samples were measured and the entanglement shrinkage values were calculated from the following formula

relaxed area -

table V

Polymercaptan (£>) Polyolefin {%) catalyst

A 2.7 A 2.7

not treated

X 0.27 (BzO) ₂ X 0.27 IPPDC

Relaxation compression shrinkage

2.5

9 4-

13.2

5.0

4.6

, 7

4098 12/1115

Example 14

A Y / olle / polyacrylonitrile (7O / 3O) mixed fabric with a weight of. 380 g / ia was treated with a trichlorethylene solution containing 0.5% poly mercaptan A, 0.1 % polyolefin A and 0.04 % diethylenetriamine up to an absorption of 300 # minutes dried at 80 ⁰ C. the sample and a non-treated control sample were washed 2 nal by the method D, and their Oberflächenvcrfilzungsschruirpfen gen were determined. the treated material had a Oberflächenverfilsungssehrumpfung of 4.0%, compared to 15 »1 ° / ° for the non-treated reference material.

Example Λ $

A ^; .7ollflanellgewebe was impregnated to a pickup \ ^r on ^r / O% with a liquid consisting of 31.4 g of a 50 aqueous E.nulsion polyolefin ^ C, 28.6 g of a 50 ^ aqueous emulsion of Polymereaptan O ^ , 3 G toluene-p-sulfonic acid and 637 ε V / water consisted of 15 minutes at 80 ⁰ G. dried, then fixed (hardened) by heating at 145 C for 5 minutes. The samples washed by Method B had a surface entanglement shrinkage of 1.3 % while the untreated fabric had a surface entanglement shrinkage of 29.9%.

Example 16

A full fabric was impregnated to an absorption of 100 % with an aqueous solution containing 50 g of monoethanolamine sulfite and 5 g of monoethanolamine per liter, and then dried. This treatment served to achieve better smoothing properties. In order to make the fabric shrink-resistant, it was then up to an absorption of 80 % with

409812/1115 "BAD Ä

a composition "treated, which consists of 62.5 parts of a 40 / Sigen aqueous emulsion of polyolefin A (prepared by vigorously stirring 40 parts of polyolefin A with 10 parts of a 1 η sodium hydroxide solution and ^ O parts V / water), 70 parts of a 40 % aqueous emulsion of Polymereaptan A ₁ consisted of 20 parts of anhydrous sodium sulfate and 847.5 parts of water The fabric was heated to -120 ° C. for 5 minutes and had non-iron properties and was shrink-resistant In pants or shirts made from this fabric, permanent creases could be introduced by spraying them with the above mixture of honoethanolamine and monoethanolamine sulfite in the area to be folded before ironing.

Example 17

In the case of reel dyeing of woven or knitted fabrics, there is inside the. Risk of strand markings being formed, which are almost impossible to remove; the material can also become felty. Using the below described Process that can be used not only on pure whole, but also on mixtures with cellulose or synthetic fibers, these difficulties can be overcome:

A double-knitted fabric made of pure wool was made up to an intake of 70 pounds. impregnated with a mixture consisting of 50 parts of a 50 % aqueous emulsion of polyolefin A, 70 parts of a 40% aqueous emulsion of polymers apt on A, 20 parts of anhydrous sodium sulfite and 850 parts of water, then it was for 2 minutes at 140 C dried. The fabric was then reel dyeing under weakly acidic conditions with a reactive dye or a 1: 2 metal complex dye and dried; it did not tangle (it met IY / S Regulation 72) and was free of strand markings.

A 0 9 812/1 11 5

Example 18

A sliver of wool was soaked up to an absorption of 80 % with a liquid consisting of 70 β of a 40% aqueous emulsion of polymer aptane A, 62 g of a 40% aqueous emulsion of polyolefin A, -20 g of sodium sulfate (ITa ₂ SO ₇ .7H ₂ O) and 848 g of water and dried at 80 ° C. A textile fabric made from the treated roving met the requirements of the IWS regulation

At OJel 19

A sliver of wool was placed in a ^ shell platter (-Rück ™ washer) as follows:

Bath I: 30 g liatrium dichloroisocyanurate 2 g 80 follow acetic acid water ad 1 1 temperature 20-30 ° 0. Immersion time 15 seconds, absorption 70 %

Bath II: 10 g sodium hydrogen sulfite or sodium thiosulfate (Na ₂ S ₂ O ₃ .5H ₂ O)

Water ad 1 1 temperature 20-40 ⁰ G immersion time 15 seconds absorption 70 %

Bad III: rinsing water

Temperature 40 ⁰ C

Bath IV: 70 S of a 40% aqueous emulsion of poly mercaptan A.

60 g of a 40% aqueous emulsion of polyolefin A.

, 4 0 9.812 / 1115 BATH ORIGINAL

Water ad 11 temperature 30 ° C immersion time 15 seconds absorption 7Q %

Bath V: 20 g sodium sulfate water ad 1 1 temperature 30 ⁰ C immersion time 15 seconds absorption 70 %

The roving was squeezed out and dried. A knitted dress made from the "treated roving" met that Requirements of the X ^ S regulation

Example 20

The procedure of Example 19 was repeated this time however, the following liquids were used:

Bath I: 50 g potassium hydrogen peroxosulfate (KHSO ₁ -) water ad 1 1 temperature 5O ⁰ G. immersion time JO seconds absorption 80 %

Bath II: $ 0 g sodium hydrogen sulfite water ad 1 1 temperature 50 ⁰ G immersion time 30 seconds uptake 80 p

Bath III: 10 g anhydrous sodium carbonate V / water ad 1 1 temperature 30 ° C immersion time 30 seconds absorption 80 %

A 00812/1 11S ■■ ",.

Bath IV: rinse water
temperature
squeezed out Ms on a recording of GO

Temperature 40 ⁰ C

Bath V: 70 S of a 40 ^ strength aqueous emulsion of Polymercaptan A

62 g of a 40% strength aqueous emulsion of Polyolefin A.

20 g sodium sulfate
Water ad 1 1
Temperature 40 ⁰ C
Immersion time 30 seconds, absorption 80 %

Finally the roving was pressed out, dried with hot air at 80 C and processed into a knitted fabric; this fabric met the requirements of IV / S regulation 72.

Example 2i

A hand-knitted yarn (100 kg) was made in the form of strands (coils) in a circulation dyeing machine with a Dyed reactive dye. The dyebath was then replaced by an aqueous liquid (30C0 l) containing 5 kg of a 40 Joigen aqueous emulsion of polymers apt at A, 4.2 kg of a 40 show aqueous emulsion of polyolefin A, 2 kg of sodium sulfite and IT 5 kg of 80 frigen aqueous acetic acid contained, and the Liquid was brought to the boil within 40 minutes. During this time the polymercaptan and the Polyolefin fully exhausted on the wool. After cooling by rinsing and subsequent drying, the Yarn processed into knitted dresses with a cover factor of 1. The clothes met the requirements of IV / S regulation 7 ^ ·

"40981 2/1 1 1 S BAU ORIGINAL

Example 22

A worsted wool fabric was soaked up to an absorption of 80 % with a bath consisting of 7 ° g of a 40 point aqueous. Emulsion of polymers apt at A, 60 g of a 40% emulsion of polyolefin A, 300 g of urea, JO g of wetting agent V, 10 g of a dye (Cibacron Scarlet KP) and 540 g of water. The impregnated fabric was rolled up and packaged in a Polyäthylenhülle After 48 hours of storage at room temperature the fabric was dried for 2 minutes by heating to 120 ⁰ C, washed, spun and dried again. The fabric was dyed evenly scarlet red, was colourfast and met the requirements of IY / S regulation 71. Instead of the scarlet dye, other dyes which are suitable for wool, in particular reactive dyes j, could also be used.

Example 25

In a Garnfärbevorrichtung were wetted 100 kg V / o11garn in 3000 1 of water at 40 ⁰ C. Then 5 kg of a 40% aqueous emulsion of Polymercaptan A, 4.2 kg of a 40% aqueous emulsion of polyolefin A, 2 kg of sodium bisulfite, 3 kg of 80% aqueous acetic acid and 2 kg of a dye (Cibalan Brilliant Red BL ) added and the whole was heated to the boil over a period of 60 minutes and held at this temperature for 60 minutes. Finally the yarn was spun and dried. A knitted fabric made from the treated yarn was dyed real red and met the requirements of IWS regulation 71.

Although the invention has been preferred with reference to FIG Embodiments explained in more detail, but it is clear to the person skilled in the art that it is not limited thereto, but that these can be changed and modified in many ways without thereby departing from the scope of the present invention is left.

409812/1115

Claims (1)

Claims 1 · Method of surface treatment of keratinous Material j characterized in that one (1) the material is ^{treated with a polyene with 1} at least 2 ethylenic double bonds each in ß-position to an oxygen, nitrogen or sulfur atom per average molecule, (2) the polyene on the material hardens or crosslinks by reaction with a polymercaptan that · per average molecule has at least 2 mercaptan groups and has the following merlanals: (a) the sum of the mercaptan groups and the ethylene groups Double bonds in the polyene is more than 4-, (b) it contains in the molecule (i) either the residue of a polyhydroxy alcohol remaining after its alcoholic hydroxyl groups have been removed or the polyacyl radical of a polycarboxylic acid, (ii) at least 2 chains bonded to such a radical via ether or ester oxygen atoms, each of which the residue of a dihydroxy alcohol or the diacyl residue remaining after the removal of both hydroxyl groups a dicarboxylic acid, (iii) an acyl radical of an aliphatic mercaptan carboxylic acid or a residue of an aliphatic mercaptan alcohol after the removal of a hydroxyl group attached to the residues via ether or ester oxygen atoms of a dihydroxy alcohol or a dicarboxylic acid is, wherein the total weight of polyene and polymers apt is 0.5 to wt. % of the treated keratinous material. 4 0 9812/1115 23A3620 2. The method according to claim 1, characterized in that that the sum of the mercaptan groups in the polymercaptan and the ethylene double bonds in the polyene is 5-8. 3. Method according to claim 1 or 2, characterized in that that the amount of polymercaptan used is so large that it is 0.8 to -1.2 per ethylenic double bond of the polyene Mercaptan groups supplies. 4. The method according to any one of claims 1 to 3j, characterized in that that the treated tissue is at a temperature is heated within the range of 35 to 180 ° 0. 5. The method according to any one of claims 1 to 4, characterized in that that deis Polymercaptan and the polyene applied in the form of a solution in an organic solvent v / earth. 6. The method according to any one of claims 1 to 4, characterized in that that the polymercaptan and the polyene are applied in the form of an aqueous emulsion by scooping out. 7. The method according to any one of claims 1 to 6, characterized in that that. a polyene is used which has a molecular weight within the range of 250 to 10,000. 8. The method according to any one of claims 1 to 7, characterized in that that a polyene is used which has at least two ethylenic double bonds each in the α-position contains a carbonyloxy group .. 9. The method according to claim 8, characterized in that a polyene of the formula is used 4 098 t2 / 1 1 1 5 - (O-alkylene) ~ 0- (CH _o CHCH „0), -R ² 2
R ¹ where mean: a is the number O or a positive number with one Value that the average molecular weight of the ■ polyene does not exceed 10,000, b is the number O or 1, c is a number of at least 1, E _{i #} the residue remaining after the removal of c OH groups from a compound with at least c alcoholic hydroxyl groups or the acyl residue remaining after the removal of c OH groups from a compound with at least c COOH groups, Alkylene is a group that has a chain of at least 2 and at most 6 carbon atoms between consecutive ones Contains oxygen atoms, / J ^ R is a group of the formula -OH or -0OCR ^, 2
R -H, an acyl group or the residue remaining after the removal of an OH group from an alcohol, with the Provided that R and R do not both represent an acyl group when a and b both represent the number 0 and da3 ρ
R does not mean a hydrogen atom when b = 1, and R ^ -H or a monovalent carbon group which can carry carboxyl or alkoxycarbonyl substituents, with a total of at least two ethylenic double bonds in the α-position to the carbonyloxy groups in the group ο
R and / or in the c groups E and / or in the bc groups ■ z R, if present, are present. 10. The method according to claim 9> characterized in that c is the number 2 or 3. 11. The method according to claim 9 or 10, characterized in that that the alkylene groups have the formula -CpH ^ - or -CvHg-. 40981 2/1115 12. The method according to any one of claims 9 "to 11, characterized characterized in that R is the monoacyl radical of a saturated one or ethylenically unsaturated mono- or dicarboxylic acid. 13. The method according to claim 12, characterized in that 2 "
that R is a group of the formula _ CO - C = CHR v / orin mean: H, -Cl, -Br or -C ^^ - alkyl and H, -COOH or a group of the formula -COO (CII ₂ CHCH ₂ O) _b - R ⁶ R ¹ R and b have the meanings given in claim 9 and R -H, an alkyl, aryl, aralkyl or alkenyl carbon mass he st off group or an alij) hatic, aromatic or araliphatic ^ means acyl group so that the group R ^ contains no more than 24 carbon atoms. 14. The method according to any one of claims 9 to 13, characterized characterized in that R ^ is a group having 2 to 16 carbon means atoms that carries either a COOH group or an alkoxycarbonyl group with 1 to 13 carbon atoms, 15. The method according to claim 14, characterized in that that R ^ is a group of the formula -CH = CHCOOH or. 0 9 8 12/1115 ORKJfNAL 16. The method according to any one of claims 9 to 15}, characterized in that R is an aliphatic radical having up to 60 carbon atoms. 17. The method according to claim 16, characterized in that that R is a saturated hydrocarbon radical up to 6 Means carbon at oiaen. 18. The method according to claim 8, characterized in that a polyene of Porrnel is used • (O-alkylene) -O- (CH ₀ CKCHoO) ^ - R ² R ¹ wherein R den remaining after removal of c OH groups from a compound having at least c phenolic hydroxyl groups Radical means, a and b has the meanings given in claim 9, c has the meanings given in claim 9 or 10 has, alkylene has the meaning given in claim 9 or'.H has, R has the meaning given in claim 9, ρ
R the meaning given in one of claims 9, 12 and 13 ■ 5 has processing and Ίτ has the meaning given in one of claims 9j 14- and 15. 19. The method according to claim 18, characterized in that R denotes a residue of Cornel 409812/1115 where "mean: 7th
E ~ H, -Cl, -Br or an alkyl or alkenyl group with 1 to 9 carbon atoms, E is a carbon-carbon double bond, an alkylene hydrocarbon group with 1 to 4 carbon atoms or an ether oxygen atom and u is a number from 1 to 4-. 20 »Method according to one of Claims 1 to 7, characterized in that that a polyene is used which essentially has the formula CH ₂ ^a 1 CH ₂ (OCHgCK) where mean: E is a group of the formula "-COCH = CHCCCH, -COCH = CHCOOCK ₂ Ch (OH). COCH = CHCOO (CH ₂ ) ^ CH-, or -COCH = CH _{2 2} g ₃ ^ where in this case a ^, a number with an average V / ert of 22.3, or a group of the formula -CH ₂ CH (OH) CH ₂ OCOCH = CHg, where in this case a ,, a number with a means an average value of 3.5, or a group of the formula -CH ₂ CH (OH) -CHgOCOC (CH ₅ ) = CH ₂ , in which case a ^ is a number with an average value of 3.5 "to 22 , 3, or a group of the formula -CO (CH ₂ ) ₂ C00CH ₂ CH- (OH) CH ₂ OCH ₂ CH = CK ₂ , in which case a ^ is a number with an average value of 5.2 means, 4098 12 / 1.1 15 or one of the-following formulas has -j- ■ (CH ₂ ) ₂ 0C0CH = CHC00CH ₂ CH (0H) CH ₂ 0 (CH ₂ ) ₃ CH ₇ "! , 0 (CH _{2) 2} 0C0CH = CHGOOGH ₂ CHCH ₂ O (CH _{2) 7} CH ₇ OCOCH = CHCOOE where in this case E is -H or -CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₇ CHL ", H ₀ CH I - (CH ₀ ) ^ OCH ₀ Ch (CH) CH ₀ OCCC CCOOCH ₀ CH (Oh) CH ₀ O- 2 ^ 4-2 OCO (CHp) pCOOCHpCH (OH) CH ₀ OE where in this case E ~ COC (CH ₃ ) = CH ₂ or -CH ₂ CH = CH ₂ , CH _{2) 2} C00CH ₂ CH (OH) CH ₂ OCOC (CH ₇₎ = ₂ ) ₂ D- - COOCH ₂ CII (OH) CH ₂ OCOG (CH ₇ ) = C wherein D represents the C ₃ JB ₇₀ & residue ^he dinerisierten linoleic acid after the removal of both carboxyl groups, H ^ CHCOOCH ₀ CH (Ch) CH ₀ OCH ₀ CH = CH 0 98 12/1 1 -OCH ₀ CHOCOCh = CHCOOH E: v / obei in this case E -CH ₅ or -CH ₃ "means, -CH = CH CO- or which is diallyl phthalate. 21. The method according to any one of claims 1 to 7 »characterized in that that the polyene triallyl isocyanurate, diallyl-unin or a compound of the formula is used H-CH ₂ CH I 0 (CH ₀ ) ,, 0OCCH = CHCO- 0C0 (CH _o ) _o C00CH _o CH (OH) CH ₂ 0CH ₂ CH = CH ₂ ) ₂ where a ^ means a number with an average fourth of 2.9, bC 0 (CH ₀ CH ₂ O) ₀ OCOCH = CHCO JO ((CH ₂ ) ₂ 0) _& H where a ^ a number nit an average ^"T ert of 13.2 means CH, CH O ₅ H ₆ -TO (CH ₂ CHO) _a OCHH ) r \ NHCOHH (CH ₂ CH = CH ₂ ) ₂ -TO (CH ₂ CHO) _a OCHH ) r \ NHCOHH (CH ₂ CH = CH ₂ ) where a ^ is a number with an average value of 5.8 means, 409812/1115 j ■: ■ - -J ₁ * r; i, / ² '- *! or -4- (CH) 0 ((CiI) .O) IC έ. C. Mr. On i- ^ / -J ₂ where a, -, a number with an average value of 6.3 means. 22. The method according to any one of claims 1 to 17 and 20, characterized in that a Polymercaptän with an average Molecular weight of at least 400 and at most 10,000 is used. 23. The method according to any one of claims 18, 19 and 21, characterized in that a Polymercaptän with an average Molecular weight of at least 400 and at most 10000 is used. 24. The method according to claim 22, characterized in that a polymercaptan is used which has not more than 6 mercaptan groups contains per molecule. 25. Verfaliren according to claim 23> characterized in that a polymercaptan is used which has no more than 6 mercaptan groups contains per molecule. 26. The method according to claim 24, characterized in that a polymer captain. the general forraei is used - (O-alkylene ^ OH (O-alkylene).
where mean: Alkylene has the meanings given in claim 9 or 11, d is a number from 2 to 6, e is the number 0 or such a positive number that (d + e) ^ -. 6 409812/1115 £ a positive number in the respective chains d and e can have different degrees, g is the number O or T, q: B ^ the est of a polyhydroxy alcohol after removal of (d + e) alcoholic hydroxyl groups and X is an aliphatic radical which has at least one mercaptan group having. 27. The method according to claim 25 »characterized in that a Polymercaptän of the general formula is used (O-alkylene) _f OH Alkylene) .0 (00) where mean: Alkyl en the meanings given in claim 9 or 11, d is a number from 2 to 6, e is the number O or such a positive number that (d + e) a positive number that can have different values in the respective chains d and e, the number O or 1, the est of a polyhydroxy alcohol after removal of (d + e) alcoholic hydroxyl groups and an aliphatic radical containing at least one mercaptan group having. 28. The method according to claim 26, characterized in that the Polymex'captan also has the formula 4 0 9 812/1115 BAD ORIQtNAU R- (O-alkylene) "OH 2343S2Q "(O-alkylene) ^ O-CO- wherein R, d, e and f have the meanings given in claim 26 have, "alkylene has the meaning given in claim 9 or 11 and h is a number from 1 to 24-. 29. The method according to claim 27, characterized in that the polyniercaptan also has the formula "(O-AlkyleiO-.OH (O-alkylene) _f 0 wherein R, d, e and £ have the meanings given in claim 26, alkylene has the meanings given in claim 9 or 11 and h is a number from 1 to 2J \ . 30. The method according to claim 28, characterized in that the Polynercaptan also has the formula _j (O-alkylene) _f O-CO-CE ₂ .SH wherein R ' and f have the meanings given in claim 26 alkylene have the meanings given in claim 9 or 11 Has, j is the number 1 or 2 and
k is a number from J to 6. 31. The method according to claim 29 »characterized in that the polymercaptan also has the formula 12/1 115 - (O-alkylene) -0-CO-CH ₀ . SH ι « 3'-o wherein Ιϊ "and f have the meanings given in claim 26 to have. Alkylene has the meanings given in claim 9 or 11 has, j is the number 1 or 2 and k is a number from 3 to. 32. The method according to claim 30 j, characterized in that that the polymer aptane also has the formula CH (OC II _O ) -0-CO-CH ₀ .SH m <£ ra f Q 2j ■ (OC I *) -O-CO-0 .H ₀ .SH 2 ^v m 2m'f .1 2, n -OO-O B ₂ bra ■ H CII _CH ₂ wherein f has the meaning given in claim 26, j the has the meaning given in claim 30 and m is the number 2 or 3 means. or 33 · The method according to claim 31 »characterized in that that the polynercaptan also has the formula CH, - (0C E ^v m CH, or 0 9 8Τ2 /: 1η1 1S 8AD ORlGiNAU CH ₂ -CH - CH-- ~ 76 - wherein f has the meaning given in claim 26, j. has the meaning given in claim 30 and m means the number 2 or 3. Process according to Claim 33 _}, characterized in that the polymer has apt to the formula CH ₂ - CH- (0C ₃ H ₆ ) _f 0C0CH ₂ SH - (0O ₂ H ^) - OOOOH ₀ SH y ο 1 d ) _f OCOCH ₂ SH Y / orin £ has the meaning given in claim 26 and has a molecular weight within the range from 700 to 6,000 to v / e. 35 · Method according to claim 33> characterized in that the polymercaptan has the pomel CH ₂ (OC ₇ H ₆ ) _f OC OCH ₂ SH CH-CH, OCOCH ₂ SH ■ (OC ₅ H ₆ ) _f OCOCH ₂ SH v / orin f has the meaning given in claim 26, tmd a Molecular weight within the range of 700 to 6000 having. 0 9 8 1 2/1115 36. The method according to claim 26, characterized in that a polymer apt is used on the lOrnel R- , (O-alkylene) -OH (O-alkylene) -0OH ₀ CHCH ₀ SH _R .w -, ΊΟ where R is -0Π or - (O-alkylene) OH, Q ⁿ R, d, e and f have the meanings given in claim 26, alkylene have the meanings given in claim 9 or 11 and η denotes a number of at least 1 which can have a different Y / ert in each of the chains d. 37 · The method according to claim 27 _1, characterized in that a polynercaptan of the formula is used. 0K ■ (O-alkylene) 10OH ₀ CHCH ₀ SH ^{f 2} £ 1O ² V7orin r " ¹⁰ -OH or - (O-alkylene)" OH means Q ⁿ R- ^ ₁ d, e and f have the meanings given in claim 26, Alkylene has the meaning given in claim 9 or 11 and η is a number of at least i in o'eder der Chains d can have different fourths. 38. The method according to claim 36, characterized in that that the polymer apt an also has the formula LIl ⁵ (O-alkylene) .OCII ₀ CHGH ₀ OH R ^{| U} worm R ^ and f which are given in claim 26. Have meanings, alkyls given in AnsOruch 9 or 11 10
Has meaning, R has the meaning given in claim 36 and k has the meaning given in claim 30. 39 · The method according to claim 37 »characterized _} that the polymer apt an also has the poleline 1 · (O-alkylene) -OCH ₀ CHCH ₀ SII R ¹⁰ __ wherein r "and f have the meanings given in claim 26 to have, Alkylene has the meaning given in claim 9 or 11, R has the meaning given in claim 36 and k has the meaning given in claim 30. 40. The method according to claim 38, characterized in that that the polymer has apt to also have the poriael _f OCH ₂ CHCH ₂ SH OH ~~ " «QfNAL wherein ε "and f have the meanings given in claim 26 to have, k has the meaning given in claim 30, m has the meaning given in A _nS p _ruc h 32 and η has the meaning given in claim 36. 41. The method according to claim 395, characterized in that that the polynercaptan also has the formula (OC _n H _2n ) _£ OCH ₂ CHCH ₂ SH OH ) _f OCH ₂ CHCH ₂ SH wherein E ^ and f have the meanings given in claim 26 to have, k has the meaning given in claim 30, m has the meaning given in claim 32 and η has the meaning given in claim 36 » 42. The method according to claim 40, characterized in that the polynercaptan also has the JFornel CH ₀ - (0C-JL-), .0CH ₀ CHCH ₀ SH Id 2 ο χ d \ d OH CH - (OC-JL-) .0CH ₀ CHCH ₀ SH 1 3 Ό 1 d \ d I OH - (OC ₇ H ₆ ) _f OCH ₂ CHCH ₂ SH OH. A0981 2/1115 23 A3 wherein f has the meaning given in claim 26, and a molecular weight of at least 700 and at most 6000 has. 43. The method according to claim 41, characterized in that that the polymer aptane also has the formula CH - (OC ₇ H), OCH ₀ CHCH ₀ SH pox cL \ d. ) _f OCH ₂ CKCE ₂ SH OH CH L \ OH CK OH wherein f has the meaning given in claim 26, and has a molecular weight of at least 7 ° 0 and at most 6000. 44. The method according to claim 24, characterized in that that a polyester having the average formula is used as the polynercaptan where mean: q. and r, which are not equal, the number 0 or 1, ρ a positive number of at most 6, Z is a divalent organic radical which has one or several of its carbon atoms with the specified -0- or BAÖ OFUG -CO units connected, X is a divalent organic radical, which by one or more of its carbon atoms with the specified SH group and is connected to the indicated -O- or -CO-units, and W is an organic radical which must contain at least one SH group if ρ = 1, and through one or more of its Carbon atoms with the indicated -0- or -CO-units is connected. 4-5 · Process according to Claim 25 ^, characterized in that a polyester of the average formula is used as the polymercaptan where mean: q and r, which are not the same, the number O or 1, ρ a positive number of at most 6, Z is a divalent organic radical which has one or several of its carbon atoms with the specified -0- or -CO units connected, Y is a divalent organic radical which has one or several of its carbon atoms are connected to the specified SH group and the specified ~ 0 or -CO units, imd V / an organic radical which must contain at least one SH group if ρ = 1, and several of it via one or more Carbon atoms with the specified -0- or -CO units connected is. 46. The method according to claim 4A, characterized in that that such a polymer is also used as a polymercaptan essentially has one of the following formulas ^ 09812/1115 ^ O ORIGINAL R ¹ 5j_ CO-OR ^{12 O-GO-R16} SHJ I- ε T ο J-CO-R ¹¹ -CO-OR ¹² -ol_ CO-R ¹⁶ SH UL- J _t _l 0-R ¹⁵ SH R ¹⁵ J- O -L CO-R ¹¹ -CO-OR ¹² -0- | - CO-R ¹¹ COO-R ¹ R '-q-coJ-oR ¹ ^ o-co-R ¹¹ -co 0-R ¹² OCO-R ¹⁶ SH , 12, H 4- 0-R ¹² -O-C0-R ¹⁴ -C0-L OR ' ¹ ^ UH - -'s HSR ¹⁶ -CO-OR ¹² -0-P-COR ¹⁴ COOR ¹² OT COS ¹⁶ SH where mean: R is the remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after removing the two -COOII- Groups, B the residue of an aliphatic, araliphatic or cycloaliphatic diol after removal of the two hydroxyl groups, E ^ an organic residue which contains at least two carbon atoms and is connected via its carbon atoms directly to the specified ester chains with terminal mercaptan groups, E is the remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid containing a mercaptan group after. Removal of the CCOH groups, ■ fc a number of at least 1, s a number of at least 2, R ^ -SH the remainder of a Monomercaptanmonohydroxyalkohols after 4 0 9 8 12/1115 BATH ORIGINAL Removal of an alcoholic hydroxyl group and E -SH the Eest of a Monomercaj Removal of a carboxyl group E-SH the Eest of a Monomercaptanmonocarbonsäure after 47. The method according to claim 45, characterized in that that a polymer aptane is used which essentially also has one of the following formulas 13Γ ¹¹ 15 Ί
E ¹ ^ Lo-CO-R-CO-OR '- ³ SH L Js KO-R ¹² O-CO-R ¹⁶ ShI J ε 0 CO-E ¹¹ -CO-OE ¹² -04- CO-E ¹⁶ SHj I— Jt Js R ¹ 14-CO-J- 0 ~ E ^{1 2} ^ -CO-R ¹¹ CO - | -. 0-R ^{1 1} ^ L oJ-CO-E ¹¹ -CO-OE ⁱ² -OJ_ CO-E ¹¹ COO-E ¹⁵ ShI L L - Jt -J R ¹ I IL CoX 0-E ¹² ^ O-CO-E ¹¹ _C0 {- 0-E ¹² OCO-E ^{1 6} Sh1 LL .Jt J H-4- 0-E ¹² -0- ^{CO-R 14} -C0 i-OR ¹² OH HSS ¹⁶ -CO-OE ¹² -0-f- COE ¹⁴ COOe ¹² OJ— COE ¹⁶ SH where mean: R is the remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after removal of the two CCOH groups, E the Eest of an aliphatic, araliphatic or cycloaliphatic Diol after removal of the two hydroxyl groups, 13 ■ '- "* ■ · E ^ an organic having at least 2 carbon atoms A 0 9 8 1 2/1 1 1 5 234362G Remainder, which has its carbon atoms directly with the specified Ester chains are connected to terminal llercaptan groups, 14-R is the remainder of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid containing a mercaptan group after removal of the COOH groups, t is a number of at least 1, ε is a number of at least 2, R - ^ - SH the remainder of a Konomercaptanmonohydroxyalkohols after Removal of an alcoholic hydroxyl group and R -SH the remainder of a monomer cap " Removal of a carboxyl group. R -SH the remainder of a Monomercaptanmonocarbonsaure after 48. The method according to claim 46, characterized in that that a polymer aptane is used which essentially also has one of the following formulas ¹⁵ J-OCO-R ¹¹ -CO-OC H ₀ SHI L ^{m 2 m} J ¹ ^ J CO-OR ¹² ~ O-CO-C .H ₂ .SH ~ | R ¹ ? ? LO Jl_ CO-R ¹¹ -CO-OR ¹² -0J CO-C .H ^ .SH ~ | LL Jt ° ^Q J R ¹ ^ JL. oJL.CO-R ¹¹ -CO-OR ¹ ^ oLLcO-R ¹¹ -COOC H ₀ SHj LL Jt m 2m J R ¹ 5-L- eof 0-R ¹² ^ O-CO-R ¹¹ CO LL OC H ₀ , SH ~] LL Jt ^{E ώ} J s CO-Lo-R ¹² -O-CO-R ^1/1 -C04-OR ¹² -O-C00 .H _n .SH L J-h α ^ o HJ-OR ¹² -0-CO-CH _o CHCO-OR ¹² OH L ^ i ίο SH ■ - * ° HS-CH _0. -CO-OR ¹² -0 CO-CH ₀ CIICO-OR ¹² O L 4w ^ 09812 / 1T15 CO-C. IU , SH v / orin R, R, R ^, s and t are given in claims 4-6 Have meanings j has the meaning given in claim 30 and m has the meaning given in claim 32. 49 »The method according to claim 47, characterized in that the polymercaptan used also essentially a of the following lOrmulas R ¹ ? X_ OGO-R ¹¹ -CO-OC H ₀ SH | -H ₀ .SH ~ | d ^ u J CO-OR ^12-0 -C0-C R ¹⁵ -C- O JICO-R ¹¹ -CO-OR ¹² -0 X-CO-C .H ₀ . SH ~] LL Jt. ³⁴ Js 0 J-CO-R ^{1 Λ} -CO-OR ¹² -04- CO-R ¹¹ -COOC H ^ SH L Jt m 2ia- R ¹ 3 Γ- GOΓθ-R ¹² -0-C0-R ¹¹ -Col 0 ( LL Jt ^m ^ J s R ¹ ? _L CoXo-R ¹² -O-CO-R ¹¹ -CoX-0-R ¹² -0-G0-C .H ₀ .SI LL Jt ο ο HX- 0-R ¹ ^ 0-CO-CH ₀ CHCO X-OR ¹² OH SH HS-C .H _0. -CO-OR ¹² -oJ- CO-CH ₀ CHCO-OR ¹² 04-CO-C .H ₀ .SH o 2a L 2, Jt ^ ¹¹ wherein R, R, R, s and t are as recited in claim 46 Have meanings, j the ^ claim 30 has given meaning Lind 'm has the meaning given in claim 32. 50. The method according to any one of claims 46 to 49, characterized 409812/11 15 indicates that R (a) is a saturated aliphatic hydrocarbon group with 2 to 10 carbon atoms, which can carry an SH group, (b) a cycloaliphatic-aliphatic Hydrocarbon group with 5 to 34 carbon atoms, which can be ethylenically unsaturated, or (c) a mononuclear arylene hydrocarbon group with 6 means up to 12 carbon atoms. 51 · Method according to one of claims 4-6 to 50. thereby Ί2 characterized in that R is a saturated aliphatic hydrocarbon means chain with 2 to 2 ^ 0 carbon atoms, those substituted by Kethyl groups and SH groups and by Ether oxygen atoms and carbonyloxy groups may be interrupted can. 52. The method according to any one of claims 4-6 to 5I) thereby marked, <iaß S ^ if it is directly with an -O unit is linked, a saturated aliphatic hydrocarbon chain with 2 to 25Ο carbon atoms, which through Methyl groups and SH groups substituted and by üthersauerstoffatone and carbonyloxy groups can be broken, and then, if it is directly attached to a -CO unit, (a) a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms that an SH group can carry, (b) a cycloaliphatic-aliphatic hydrocarbon group with 5 to 51 carbon atoms, which are ethylenically unsaturated or (c) is a mononuclear arylene hydrochloride group having 6 to 12 carbon atoms. 53. The method according to claim 24, characterized in that as polymers apt to the tris (thioglyl: olate) of polyoxypropylenetriols with an average molecular weight of 600 to 4000, a glycerine-propylene oxide adduct with ethylene oxide end groups and an average molecular weight of 5,000, a hexane-1,2,6-triol-propylene oxide adduct with one 812/1115 average molecular weight of 1500, a 1,1,1-trimethylolpropane-propylene oxide adduct with an average molecular weight of 4-040, the bis (thioglycolate) of an adduct of butane-1,4-diol and tetrahydrofuran with an average molecular weight of 1000 or a polyoxypropylene triol with an average molecular weight of 4000, the tetrathioglycolate of an adduct of pentaerythritol with propylene oxide with an average molecular weight of 4000 or an adduct of ethylene diamine with propylene oxide with an average molecular weight of 50O ₅ the tris (2-mercaptopropionate) of a polyoxypropylene triol an average molecular weight of 4000, a poly (2-hydroxy-3-mercaptopropyl) ether of a polyoxypropylene triol with an average molecular weight of 4800, a polyester containing mercapto succinic acid and butane-1,4-diol or polyoxypropylene glycol units, a thioglycolic acid unit having r polyester with a polyoxyethylene glycol, polyoxypropylene glycol, butane-1,4-diol or diprimary alcohols, produced by catalytic hydrogenation of methyl esters of aromatic-aliphatic fatty acids, as the alcohol component and trimerized linoleic acid or mercaptosuccinic acid as the acid component, a 2-mercaptoethanol units E is ender polyester with a pentaerythritol propylene oxide tetrol adduct or a polyoxypropylene tetrol as the alcohol component and adipic acid, succinic acid or a dimerized linoleic acid as the acid component, 3-mercaptopropionic acid with butane ~ 1 . _t 4-diol and a trimerized linoleic acid, thioglycolic acid or J-mercaptopropionic acid with 2 alcohols from the group glycerol, butane-1,4-diol, hexane-1,6-diol, hexane-1,2,6-triol , the polyoxypropylene triols, polyoxypropylene glycol, 1,1,1-trimethylolpropane, the mixed diprimary alcohols produced by the catalytic hydrogenation of methyl esters of aromatic-aliphatic fatty acids, 2,2-bis- (p-hydroxypropoxyphenyl) propane and an acid from the group adipic acid , diinerized linoleic acid, phthalic acid 409812/1115 and succinic acid, which is a n-pentanol terminated polyoxypropylenetriol units with mercaptosuccinic acid Polyester or a polyester comprising units from a polyoxypropylene glycol, mercaptosuccinic acid and adipic acid terminated with acetic acid is used. 54. The method of claim 1, wherein the polyene and the polymercaptan in the presence of a Brönsted base as a catalyst be used. 55. The method according to claim 1, characterized in that the polyene and the polymercaptan in the presence of a Brönsted acid or a free radical generating catalyst can be used. 56. The method according to claim 54, characterized in that the catalyst is based in an amount of 0.1 to 20% by weight based on the total weight of polyene and polymercaptan. 57. Keratin-like material, characterized in that it is 0.5 to 15% by weight, based on the weight of the keratin-like Material, a product of a polyene according to claim 1, and a polymercaptan according to claim 1, contains. 58. Keratin-like material according to claim 57, characterized in that that the polyene in the presence of a Brönsted base, a Brönsted acid or a free radical yielding Catalyst has been crosslinked or cured with a polymercaptan. 409812/1 1 1 5