DE2138448A1 - Treatment of materials containing keratin - Google Patents

Description

The "present invention relates to a method of modification of keratinous materials. In particular, it relates to a method of making the material resistant to shrinkage and to give the product permanent ironing properties to lend.

It is an improvement or modification of the invention; in the the parallel application P Γ9 34 678.2 of July 9, 1969 is described and claimed. ... "

A number of methods are known to remove keratinous To make materials shrink-proof, with some

.209808 / 18.97-

of them to the material in tissue or fiber form a resin product is applied. The procedures for enema fix the dimensions of the keratinous material than stabilized against shrinkage caused by fungi.

Process to give keratin-containing materials permanent ironing properties to lend are also known. Many of them use the same or similar resins, as used in enema mooring procedures. In some methods of non-iron finishing, the keratin-containing material is given the desired shape before curing of the resin awarded. The resin is then allowed to harden while the material is in the desired porin, e.g. B. in Porm of iron or Pleats are kept. In other methods, the resin is applied after the material to be treated desired porm awarded v / urde. Thanks to the non-iron finish one stabilizes the porin and surface softness of the material against deformations that can be caused by aqueous solutions. The desired Porm can be in front of or in front of the material after treatment with the resin by the Pachmann well-known methods which involve the use of agents such as water vapor, reducing agents and bases.

It is desirable, but not essential, that the after Process for imparting dimensional stability and fastness to ironing treated keratin-containing materials in household washing machines can be washed. To wash in washing machines

2 0980 8/1897 - 5

In order to be able to see, the material must be treated applied layer violent movements in warm or hot '* Can withstand water containing detergent; these requirements require "a tough test for the shrink-proof, Wrinkle-proof and non-iron finish. , ·

One of the ". Keratin particularly attractive properties · fibers" and especially wool. Is their excellent grip, an important disadvantage of mit.vielen of the resins used for Schrumpffest- _T Knitterfest- and non-iron equipment is connected, is the hard grip, given to the pastes and gifts containing them. Attempts have been made to overcome the hard feel by using plasticizers, but this has not been successful in some cases because the plasticizers often reduce the effectiveness of the resins. \

In the patent application FI934678.2 is a method for treatment of materials containing jceratin, which consists in that the material is treated with a Polythiolhars that at least two mercapto (thiol) groups per molecule and ■ "(a.) The remainder of a polyhydric alcohol,

(b) at least two polyoxyalkylene groups connected to this radical :, τ chains and

(c) by oxygen atoms with carbon atoms of this poly ^ .:. osgralkylen chains connected at least two acyl radicals . .a mercapto (thiol) group-containing aliphatic

2 09 80 871897 '

Carboxylic acid and / or at least two radicals of a mercapto (thiol) group-containing aliphatic alcohol after removing a hydroxyl group, and curing the resin on the material. In this procedure, with which the treated material is made resistant to shrinkage and is given permanent ironing properties . does not adversely affect its grip. The resins harden, i.e. H. react on the keratin fiber, whereby the hardening speed can be regulated by selecting a suitable catalyst. The catalysts used are organic and inorganic Bases, siccatives, free radical catalysts or oxidizing hardening agents are proposed. as specific examples of the siccative are calcium, copper, iron, lead, ger and cobalt naphthenates. the More effective, of these catalysts are primary and secondary Amines, however, often affect the treated material when they are used

an undesirable odor. is imparted.

"It has now been found that the curing of the polyoxyalkylene resins with terminal mercapto (thiol) groups on the keratin-containing materials by means of certain metal-containing salts and Complex compounds can be accelerated; if such products are used as a catalyst, the treated material shows al in general -no undesirable. odor and. is the curing speed. often faster ,, than-if the earlier proposed Catalysts are used.

20 9 808/1897 '~ ⁵ ~

The present invention thus relates to a method for Modification of materials containing keratin by treating the material with '

(1) a resin that has at least two mercapto (thiol) groups per molecule and · · ■:

(a) the remainder of a polyhydric alcohol,

(b) at least two polyoxyalkylene chains connected to this radical and ·

(c) by oxygen atoms with carbon atoms of these polyoxyalkylene chains connected at least two acyl residues of a mercapto (thiol) group-containing aliphatic Carboxylic acid and / or at least two residues of a mercapto (thiol) group-containing aliphatic alcohol having after removal of a hydroxyl group and

(2) a curing catalyst

and curing the resin on the material; the invention The method is characterized in that as a curing catalyst either a heavy detail salt and a non-drying one Acid with an acid strength (-log pK) of less than 5 or, a chelate of a heavy metal including the chelates representing salts are also used, whereby "heavy metal" has the following meaning “.

The present invention further comprises keratin-containing materials: alien that have an above-mentioned polymer, mercapto (polythiol) resin and an above-mentioned catalyst on the surface

- 6 209808/1897

carry sator, which is cured in the presence of said catalyst or is still curable.

The polythiol preferably has three to six mercapto- (thiol) Groups per molecule. Particularly good results are achieved with Resins achieved · that have three or four mercapto (thiol) groups per Exhibit molecule.

Preferred polythiols are those of molecular weight between 400 and 10,000, especially those with the general formula

40-alkylene) _m 0H

Jq-1

where η, ρ and q represent whole positive numbers, m is an integer of at least 1 and Xn can have different values in the p and (q-1) chains,

ρ is at least 2 and at most 6,

q is such a number that

{p + qj is at least 3 and at most 7, each of the "alkylene" radicals is a chain of at least 2 and at most (5 carbon atoms between two successive oxygen atoms,
R is an aliphatic radical with at least 2 carbon atoms

and '_ ₇ _

209808/1897

X is an aliphatic radical with at least one mercapto- (thiol) Group "mean.

The oxyalkylene radicals in the individual polyoxyalkylene chains can be different from each other and can e.g. B. substituted with phenyl or chloromethyl groups.

Partly or completely esterified compounds can thus be used formula

40-alkylene) _m 0H

q-1

40-alkylene) _m 0. CO.

II

where B, "alkylene", m, ρ and q have the same meaning as in Formula I and r is a positive integer up to 18 or even 24 can be used. More preferred esters correspond the formula

■ fÖ-alkylene) _m OH

q-1

■ fO-alky 1 en) _m 0. CO.

III

wherein "alkylene", m and q have the same meaning as in formula I.

to have, . ,

u is a positive integer of at least 2, is an integer of at least 3 and at most 6, such a number that

(P ₁ + q) is at least 4 and at most 7 and "... ■ 209808/1897

IL. an Allphatlian remainder-with; at least: 5 tend at most. · 6i ■■: ·; - ■ "carbon atom en- is .., _ä ... "-; --.- . ■ - ■■■ --.-: ■, - ■, .. ■: ■■■ . ■; .--- - _: -, -

direct preferential -Esterers eiitspreciiert the

. CO. «^

IV

where "alkylene", m »p ^ imd τχ the same. Be.deMtEmg. as in
Formula IU have and.

Ep is an aliphatic · hydrocarbon radical with at least &; 5 '
and. at most / 6. carbon atoms is ... ·. '^; . ^; /.

Next; l) epreferred. are. Esters based on τοη glycerine ,. Fexan 112,5 - tri.pl or hexane-1 j2,6-triol urxd ethylene and / or 'propylene oxide, dt h. Esters of the formula · - · ·; ♦ ^"·:; - ■ '.' -. ^; "

f CH

CH ₂

-H

_m 0.

f 2 ~ ^ ^0C At ^ m 0 · CO H _2t ) _m 0.C0

209808/189 7

, V

Vi

-worin m rand u have the meanings indicated -vorsteheind have and It -from an integer of at least 2 and at most 3 Is *

Me abovementioned polyoxyalkylene ster with -terminal Mercapto -; (! Ehiol) groups are easily diarch IJiasetziimg of a polyvalent Alcohol with an alkylene oxide and subsequent esterification of the acidic hydroxyl groups with a mercaptocarboaic acid eriiältllch.

Suitable polyhydric alcohols are ethylene glycol, polyoxyethylene glycols, Iopylene glycol, polyoxypropylene glycols, propane-1,3-diol, Polyeplchlorhyärliie, Butaö-1,2-diol, Butane-1,3-diol, Butane-1,4-diol, butane-2,3-diol, poly (oxy-1,1-dimethylethylene) glycols, Polytetrahydrofurans, glycerine, 1,1,1-irimethylolethane, 1,1,1-trimethylolpropane, hexane-1,2,5-triol, hexane-1,2,6-triol, Pentaerythritol, dipentaerythritol, mannitol, sorbitol and adducts of Alkylene oxides with ammonia or amines such as diethanolamine and Tetrakis (2-hydroxyethyl) ethylenediamine. Suitable alkylene oxides Binds ethylene oxide, propylene oxide and, less preferably, the butylene oxides, epichlorohydrin or tetrahydrofuran. If desired, can polyhydric alcohols with an alkylene oxide, e.g. B. treated propylene oxide and then with another alkylene oxide, how ethylene oxide can be aftertreated.

The preferred mercaptocarboxylic acids for esterification are Thioglycolic acid (2-mercaptoacetic acid), 2-mercaptoproplonic acid

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- Ίο -

3-iflereaptopropionic acid. However, other mereaptononocarboxylic acids can also be used like 2-mercaptoundecylic acid 12nd 2-kercapto Stearic acid can be used.

Especially for the purposes of the present invention preferred polythioesters are those obtained from glycerin, propylene oxide and thioglycolic acid and thus the formula

CH ₂ -

CH i
CH,

OCOCH ₂ SH OCOCH ₂ SH OCOCH ₂ SH

VII

correspond, in which m has the meaning given above, and which have a molecular weight in the range from 1,000 to 5 to have. Such resin products are commercially available.

A second group of usable polyalkylene oxides with terminal mercapto (thiol) groups are the esters of the formula

(O-alkylene) _m OH

q-1

(O-alkylene) _m OCH ₂ CHCH ₂ SH

VIII

where R _{3 is} - ^ 0H, - (0-alkylene) _v 0H, -O.CO. ^ H ^ SH or - (0-alkylene) _v 0.C0.C _u H _2u SH, R, "alkylene" _f m, p, q and u have the meanings given above. and ₂ 09808/1897 ~ ¹

ν is an integer of at least 1 included in "the various p-chains can have different values.

The oxyalkylene groups in the individual polyoxyalkylene chains can be different in the same way, but are preferably the same; they may, if desired, be substituted, e.g. B. with phenyl or chloromethyl groups. \ - '

.Bevorzugt among the ethers of Formel'-VTiΓ sind.diejenigen, further comprising the formula ^_"■;::

(O- "alkylene) _m OH

ϊ-1

IX

(0-alkylene)

R,

correspond, in which "alkylene", R ₁ , m, R ₁ , P 1 and q have the meanings given above. 7, 'pus preferred ^, are those of the Pormel

(0-alkylene)

wherein R ₂ and p .. also have the meanings given above. -. -. ^; _; ■

The particularly preferred ethers of the formula:. ^l

(OC _t H _2t ) _m OCH ₂ CHCH ₂ SH | XI

^ r ■■■ ■ ·. "■". · ■ ". ■ ■ -J - ·. '

where R ₂ , t, m and p ^ have the abovementioned meanings v '■ ■ · ;, -are-also; in Handel available ** Die, Äthör - dei · ÄBpr-r Z

2 0 9 8 0 8/1897

mel VIII, in which B, is -OH, can be known per se Way by reacting an alkylene oxide with a polyhydric alcohol, etherification of the hydroxyl groups Reaction product with epichlorohydrin and treatment of the reaction product be made with liatric hydrogen sulphide to replace the chlorine with a mercapto group (see U.S. Patent 3,258,495 and British Patent Specifications 1076725 and 1144761),

Ether of the general formula

OCH ₂ CHCH ₂ SH

^0H

where Ep, t, m, ν and p., the meanings given above are also preferred. Ether of the formula YIIl, in where E, - (O-alkylene) OH means, can thereby be prepared that the product obtained by reacting epichlorohydrin, the alkylene oxide and the polyhydric alcohol first with an alkylene oxide and then reacted with sodium hydrogen sulphide (see British Patent 1144761).

Particularly preferred ethers are those of the formula

209808/1897

CH ₀ (ΟΟ ,, Η,) OCH ₀ CHCH ₀ SH

2 ^ν 3 Q πι 2 ι 2

Oh

CH (OC ₅ Hg) _1n OCH ₂ CiICH ₂ SH XIII

OH CPI ()

I ₂

'OH

especially those with molecular weights in the range from 700 to. 3,500 and even up to 7,500.

I The ether esters of the formula VIII, in which R ₃ -0.C0.C _u H _2u SH

or - (O-alkylene) O.CO.CH means ₂ SH, of the corresponding alcohol can be obtained with a mercaptocarboxylic acid H00CC _u H _2u SH by esterification.

The keratin-containing materials can with the catalyst before, during, or, after treatment with the polythiol. treated will. , ·

■ - ■■■■■■■■■■ · ■ ■. ....... (

“Heavy metal”, the salts and chelates of which are used as a catalyst in the process according to the invention, is to be understood as a metal which is described in Lange, Handbook of Chemistry, To. . "Edition, McGraw-Hill Book Co., at pages 60-61 referred to as" hard ", is that a metal of Groups IB, HB, _f IIIÖ IVB, VB, VIB, VIIB or VIII, a metal of group IHA with an atomic number of at least 13i a metal of group IVA with an atomic number of at least 32 or a metal of group VA with

- 14 20 9 ⁸ ° - ^8/1897

an atomic number of at least ξ> 1 · Preferably - among these a metal from groups IB, HB, IVB, VB, VIB, VIIB and VIII, in particular the first series of these metals, d. h .. titanium, vanadium, chromium, manganese, nickel and especially iron, cobalt and copper. Suitable salt-forming non-drying acids are mineral acids $ especially hydrogen chloride, Hydrobromic, nitric, sulfuric, phosphoric acid and phosphorous acid and organic acids such as chloroacetic acid, fumaric acid, maleic acid, oxalic acid, salicylic acid and especially citric acid. Suitable chelating products include compounds in which the chelating agents Atoms are oxygen and / or nitrogen, for example 1,2- and 1,3-diketones such as acetylacetone, alkylenediamines such as ethylenediamine and especially ethylenediainetetraacetic acid.

The amount of the catalyst used can vary depending on the nature the polythiol used, the keratin-containing material, the desired curing speed and other factors, in wide limits fluctuate. In general, however, the amounts range from 0.1 to. 10, preferably 0.1 to 5% by weight, based on the weight of the polythiol used. The polythiol and the catalyst can be used together or separately in each applied to the keratin-containing material in the desired order will.

The treatment method according to the invention for imparting. Stability of shape and fastness to bend creates fibers or "pieces". "

2 09808/1897 '' - 15 -

that have an excellent grip and that when washed maintain their original dimensions and shape in machines. In addition, the after The method according to the invention also treats materials high crease resistance, which is an important property for luche that are used in the manufacture of trousers because very easily around the knee or the hollow of the knee in trousers Can form gaps. Of course, crease resistance is also an important property of many other items of clothing. .

In addition to preventing or delaying the growth of fungi conditional running-in prevents or delays the inventive method also the sagging running-in, which occurs with Knitwear represents a major problem. Accordingly, the method according to the invention is used in particular for anti-shrink finishing applied by knitwear.

The term "keratinous materials" used in the present specification includes all forms of keratin fibers or textiles and articles of clothing made therefrom, such as nonwovens, slivers, card slivers, noils, yarns, weft yarns, staple fibers, non-woven fabrics, woven fabrics and knitted goods. The method according to the invention is applied in most cases to piece goods or finished garments. Under certain circumstances, however, it may also be expedient and desirable to use enema solid pasers, e.g. B-. in the form of

209808/1897 "- 16 -

place. The material to be treated can either consist entirely of keratin fibers or of mixtures of these fibers with synthetic fibers such as those made from polyamides, polyesters and polyacrylonitrile or with cellulose fibers including those made from regenerated cellulose. In general, however, the material used should be at least 30 wt. Tso contain keratin fibers, whereby better results can be achieved with such materials die'zu $ 100 consist of keratin fibers.

- The keratinous materials can be natural or recycled be. Preferably, but not necessarily, they are made from sheep's wool. You can also choose from alpaca, cashmere, mohair, Vicuna, guanaco / camel hair, llama hair and mixtures of these materials with sheep's wool.

The poly thiols can be used alone or in combination with resins or resin-forming substances such as aminoplasts, epoxy resins (ie compounds with an average of more than one 1,2- w oxide group per molecule) or polyisocyanates.

Many of the foIythiols used in the process according to the invention are insoluble in water, but can be used in the form of aqueous dispersions or emulsions. she however, can also be used in organic solvents, e.g. B. lower alcohols such as ethyl alcohol} lower ketones such as ethyl methyl ketone, Benzene or halogenated, especially chlorinated and /

209808/189 7 * - 17 -

or fluorinated hydrocarbons are applied, the contain no more than three carbon atoms, like those at The solvents used for dry cleaning are carbon tetrachloride, trichlorethylene and perchlorethylene.

The amount of the "polythiol used depends on the desired Ef fect from. I ¹ Ur most purposes amounts in the range of 0.5 to 15 ° f, based on the weight of the material to be treated, is preferred. For stabilizing, are of knitwear in general from 1 to 10 wt. of the polythiol fo necessary. A high degree of shrink resistance, Ealtenfestigkeit and crease resistance may in woven fabrics with relatively small amounts, for example with 1 to 5 wt. $ be achieved. the handle of the treated material naturally depends on the Amount of polythiol used. The minimum amount of polythiol necessary to achieve the desired effect can be determined by simple experiments. In addition, the structure of the tissue also has an influence on the necessary amount of polythiol ". '

The curing of the polythiols is further accelerated by using elevated temperatures. If particularly rapid curing is required, temperatures in the range from 40 to 180 ° C can be used. The Polythiolharz and the catalyst can be applied to the keratin-containing material in a conventional manner are, for example Kamrazüge or tissue of wool to ^_s; treat, the PiOdukte can be impregnated

2 0 9 8 0 8/1897 '.-18-

BATH

ct & ß you let them change through a bath or immerse them in it. Are items of clothing or parts. Of clothing to treat, ist.es favorable to spray them with the polythiol. It is also more favorable to circulate the garments in a solution of the polythiol in an organic solvent. The machines used for dry cleaning are particularly suitable for this.

If a shrink-proof finish is to be carried out, it is generally better to apply the polythiol to the keratin-containing piece goods, although, as indicated above, it can also be applied to the fibers in the form of slivers or slivers. The tissue can "before or be smoothed after the treatment with the polythiol (" flat-setting ") In this way, the fabric is not only its original Bimensionen _s but also its smooth, soft appearance / ash during wear and after the V. It should be noted, however, that smoothing is not necessary and for some fabrics not even desirable. The smoothing or spreading is generally done so that the fiber ^: good either with steam at overpressure or with steam at atmospheric "spherical Pressure is treated in the presence of a smoothing agent and moisture, the fiber material being "kept" flat. The ^: -smoothing ·: can also be achieved by using high concentrations of a "reducing agent and a swelling agent, the fabric during the Washing off the

2 0.9 8 0 8.7 1 β 9.7 ■

bath

Γ ■:

excess agent is kept flat. In another method, hardening in the smoothed state is achieved by that the keratin-containing material with a swelling agent and an A] kanolamine carbonate, for. B. urea or diethanolamine carbonate, is impregnated, the material is then dried and semideka- is animalized.

Should the keratin-containing material be used in a non-iron finish subject, this can be accomplished in a number of ways will. One method is that the keratin-containing Material is treated with the folythiol, the material is then processed into garments or parts thereof and pleats or creases are incorporated, with reducing agents, Bases or superheated steam can be applied, -The polythiol can also be used here at springtime during manufacture the piece goods are applied to the fibers, d. H. on the fibers themselves, on the yarns or the fabrics * If desired, means can be used. the mercapto (thiol) groups of the Block wool, e.g. formaldehyde or higher aldehydes, on which creased or pleated garments are applied after the polythiol has hardened.

A preferred method of using the polythiol to achieve this a permanent ironing effect is * that a finished Garment made of keratinous fibers or a part thereof, that already has the desired pleats or creases

. - 2o 209808/1897

ORIGlNAL BATHROOM

• Has, with the dissolved in an organic solvent 'Polythiol "is treated. It is essential that the polythiol is used in an organic solvent,

because the treatment with aqueous systems is only the one already presented Pleated or creases disappear again ". With another method, the primarily only concerns the production of pleated and ironed folds that are permanently ironable, the fabric is impregnated with the polythiol where a bow or pleated fold is to be attached P. then pleats and holds the fabric in the folded state while heat and pressure are applied. .

The smoothing ("setting") of the jceratin-containing piece goods both before as well as after the treatment with the polythiol resin effected by application, usual method. For example can "Setting-agents" such as reducing agents, bases, water and superheated steam are used. Monoethanolamine esquisulphite is the most common and can be used in conjunction with swelling agents such as B. urea are used.

In another method for smoothing ( "flat-setting") and keratin to Formfestmaehen tissue treated to the Ge weave with the smoothing means ( "setting agent"), smoothes the flat-held, nor ¹ wet tissue by heating, it is impregnated subsequently with a aqueous emulsion of polythiol and des.

- 21 - 209808/1897 *

Catalyst, dries the fabric and hardens the polythiol. Finally, the fabric is processed into garments, on which pleated or ironed folds are applied by steaming in the presence of

means of a smoothing agent ("setting agent") such as monoethanolamine sesquisulpb.it be attached.

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

Cloth samples were placed in an "English Electric Reversomatic "with the machine on the Program 5 (40 ° C) and the time control is set to 1 (15 minutes of laundry). The washing liquid contains pro Liter 2 g soap flakes and 0.8 g anhydrous sodium carbonate. The liquor ratio is 1:50. After washing, the Swatch samples in a Parnall Tumble Dryer for 30 minutes dried over full heat.

The resin products used were manufactured as follows:

"Thiol Resin A"

A mixture of 800 g (0.2 g mole) of one of glycerin and propylene oxide obtained triols with an average molecular weight of 4000, 55.2 g (0.6 g mol) of thioglycolic acid, .5 g p-Toluenesulphonic acid and 350 ml of toluene are stirred into heated to boiling under a nitrogen atmosphere under reflux.

209 8 0 8/1897 -22-

10.8 ml (0.6 g mol) of water formed during the reaction are separated off in the form of its azeotropic mixture with toluene. The mixture is cooled and washed with water and the organic layer is separated. After the solvent has been separated off from the organic layer in vacuo, 793 g (94 i ° of theory ) of the desired tris (thioglycollate) ("thiol resin A ⁿ ) remain. The product has a mercapto group content of 0.59 equiv. / kg «,

• " Thiol resin B "

This product creates a poly (2-hydroxy-3-mercaptopropyl) ether denotes that of a glycerol-propylene oxide adduct with an average molecular weight of 4800, epichlorohydrin and sodium hydrogen sulphide was produced. The product has a mercapto group content of 0.32 equiv / kg.

" Thiol Resins C, D and E "

These products were prepared as described for thiol resin A, except that perchlorethylene was used instead of toluene.

209808/18 97

~ 23 -

Thiol
iiarz Polyol adduct
t description
of Her
stellers through elin.
Mole weight herges
Alkylene
oxide hands out
alcohol \ Teresterification
acid C. Ifiax LHT 112 1,500 Propylene
oxide Hexane
1.2 _S 6 ~
triplet Thioglycol
acid D. - 2,220 "Propylene
oxide Pentaery
thrit Thioglycol
acid E. Polymeg 1000 1,000 Tetrahy
drofuran Butane-
1,4-diol Thioglycol
acid

The words "NIAX" and "PQLYMEG" are trademarks. The '! FTIAX "product is from the US company Union Carbide Co. and the "POLYKEG" product available from the US company Quaker Oats. ^

example 1 ^Λ

An aqueous emulsion of the thiol resin A v was made by high speed mixing of the following products:

Thiol resin A 500 g Emulsifier 50 g water 450 g

A 50% aqueous solution of an adduct of a mixture of C ₁₆ - and CjQ-aliphatic primary amines (1 mol) and ethylene oxide (70 mol) served as emulsifier. Various metal salts, which were diluted 1:20 with water, were added to the emulsion profiles. Samples of Y / oll flannel with

2 0 9 8 0 8/1897 - 24 -

■ a weight of about 170 g / m are padded with the mixture in such a way that 3 $ of the harses are absorbed. The samples are then dried for 15 minutes at 70 ° C., steamed for 2 1/2 minutes with a steam iron and then stored at room temperature with the access of air. Compartment storage for various periods of time, the tissue samples are washed. The shrinkage is determined by measuring the fabric before and after washing. Area shrinkage: (area loss) was calculated from the values of linear shrinkage.
The results result from the following table I.

- 25 -

209808/1897

Table I.

CD CO OO CD CO

CO CO

Catalyst CuSO. CuNa ₂ FeCl,. · ' applied
Amount (f *) * ^c / o Loss of area after curing for 2 days ^: 8th days 22 days formula CuCl ₂ .2CuO.4H ₂ O ·. Pe (NOj) ₅ .9H ₂ O O "01 5 1 day ■ 7.4 6.0 *
4.0 CH ₀ COO-
⁷ 3+
HO.C-COO- Pe ⁵⁺ ■
CH ₂ COO- 0.015 8.8 6.9 3.6 4.0 -OCO-CH ₂ CH ₂ COO-
• ^ HCH ₂ CH ₂ JSr. '
-OCO-CH ₂ "" ^ CH ₂ COO- 0.0375 7 * 0 13.1 12.6 9.8. 0.015 12.6 2.5 3.0 - 0.015 4.0 10.3 ■ 4.5 4.0 0.015 9.8 12.0 5.9 8.4 11, 2

Ul

K)

OO OO

ro he »

Table I continued

CO OD O OO

catalyst FeNa CoCl ₂ .6HgO applied
Lot (#)*. fo area loss after, hardening for 2 ^! Days 8 days . 22 days Formula ^; ;; ' . \ ■. . . ■ ■, Fe ₂ (SO ₄ ) ₅ 0.035 1 day 12.6 8.4 6.4 -OCO-CH «CH ₉ COO-
\ s ^d
NCH ₉ CH ₉ N
-OCO-CH ₂ - CH ₂ COO- untreated 0.015 ■ 15.9 7.9 7.9 7.4 0.015 8.4 ' 7.4 5.0 - 6.0 23.5 23.8 23.5 22.2

Based on the weight of the wool

ro

CO CX)

- 27 -

Example 2

Yoln flannel samples were padded in a 2.3% solution of thiol resin A in 50% aqueous ethanol containing copper sulphate or iron (III) chloride in such a way that 3 ^c / ° of the thiol resin were absorbed. The samples were then dried, steamed, stored and washed as described in Example 1. The area loss of the untreated wool flannel averaged 23.5 / », while the area loss of the treated samples was as follows:

Table II

catalyst formula applied
Quantity (£) * ° / o loss of area after hardening
for 2 days , 8 days 22 days OuSO ₄ 0.015 1 day 8.8 7.5 6.9 PeCl ₃ . 0.01.5 6.5 9.3 8.9 8.4 8.8

* Based on yfolle weight

Example 3

A gray serge cloth (100 % wool) with a weight of etv / a

290 g / m was smoothed by a usual method (Jlflatset "), wherein as Glättungsraittel (" setting agent ") a mixture of 1 ^c / o monoethanolamine and 1 ^'0 J ₀ Monoäthanolaminsesquisulphit

- - 28 -

209808/18 9 7.

was used. Cloth samples were made with a like in the example 1 described emulsion of thiol resin A padded in such a way that 2 $ thiol resin A with or without the addition of Copper Sulphate Catalyst ($ 0.5 by weight of the thiol resin A) are added. The samples are then allowed to cure at room temperature and washed after 1, 3 or 7 days. The washing process was carried out for 1 hour in a domestic washing machine with a rotating drum of the Bendix MRE type using a phosphate buffer solution of pH 7 at 40 ° C carried out a weight liquor ratio of 1:22. The samples were then removed and 1 minute at a time Household drying drum wrung out. After taking them out of the drying drum, the samples are shaken vigorously three times and then shaken vigorously let them hang at room temperature until dry. The loss of area is as follows:

Table III

catalyst io area
1 day nvexlust nac
3 days h hardening for
7 days - "- 13.4 8.9 8.7 CuSO. . 2.3 3.3 3.5

Example 4
3 io of the thiol resin A were applied to wool flannel as described in Example 1. The treatment liquid were

- 29 209808/1897

the various metal salts indicated in Table IV were added. The shrinkage of the treated fabric samples was measured as described in Example 1 and the results are shown in Table IV. The loss of area of the untreated
Wool flannel was about 23 1 °. '

Table IV-

catalyst formula applied
Quantity ($) '* fo area loss after hardening for 2 days 8 days 22 days A1 ₂ (SO ₄ ) ₃ 0.015 1 day ; . - - 6.9 K ₃ Fe (CrO ₆ 0.015 14.0 _r ' 12.1 8.8 3u (iiO ₃ ) ₂ 0.0175 - 9.4 9.4 8.8 itaCl ₂ .4H ₂ O 0.015 9.4 8.4 6.0 ii (BP ₄ ) ₂ 0.015. 9.4 7.9 7.9 7.9 ^V Sr (SO ₄ J ₂ .4H ₂ O 0.015 9.4 8.8 8.4 7.9 3bF " 0.015 11, 3 11.2 .- 5.5 C ₂ Cr ₂ (SO ₄ .24H ₂ O ₄ J 0.03 11.2. ' 12.6 10.5 - 14.5

* On the basis of wool weight a

209 808/18 97

• - 30—

r- 30 -

example 5

Wool flannel is padded with a 1.11 follow solution of thio resin A in trichlorethylene in such a way that 270 fo were absorbed. The "treated cloth was dried on a tenter in its original size for 15 minutes" at 70.degree. It was then padded with an aqueous copper sulphate solution in such a way that 140 $ of the solution were absorbed, which corresponds to an absorption of 0.015 $> copper sulphate, based on the weight of the wool. The cloth was dried as indicated above, then steamed for 2 1/2 minutes using a steam iron and then stored at room temperature with free access to air. After storage periods of different length, the cloth samples are washed and the shrinkage is measured as described in Example 1.

Storage time (days) ft Loss of area after washing

0 11.2

1 7.4 untreated / 26.2

Example 6

Wool flannel was with a 1.11 solution of the follow Thiolharzes A in Trichlaräthylen which additionally 0.011 fa bis (pentane-2,4- dionato) cobalt enthiä-t, padded such that 270 ^c / o of the solution is recorded. The cloth sample is dried at 70 ° C. for 10 minutes while maintaining its original size

209808/1897

and then stored in contact with air at room temperature. For each storage period of different length, the samples were washed as described in Example 1 and the shrinkage was measured.

Storage time (days) · jo loss of area after washing

1, 7.9

"2 5.4

untreated 26.2

- Example 7

Emulsions of the thiol resins A-E were made using a high-speed mixer manufactured in the following way:

Thiol resin 500 g

Emulsifier 50 g

Sodium carboxymethyl-. ^Λ
cellulose ^ 5g

Water 445 g

The same product as in Example 1 was used as the emulsifier. '".

Y / ollflannel is padded with the emulsions diluted 1:20 with water in such a way that the thiol resin absorption is 3 "fo . The treatment liquids also contain copper sulphate or iron (III) chloride as a catalyst Retaining the original dimensions, dried for 15 minutes at 70 ° C, then steamed for 1/2 minutes using a steam iron

finally stored in contact with air at room temperature. Subject to different storage times, the samples will be as in the example 1 described washed and the shrinkage measured '. The results are given in Table V below.

Table V

Thiol
resin catalyst applied '
Quantity (£) * fo area loss after hardening for 2 days 8 days 22 days A. formula 0.015 1 day - 9.3 9.8 A. CuSO, 0.015 11.7 - 7.9 9.4 B. FeCl ₃ 0.015 * 10.3 - -; 4.0 B. CuSO. 0.015 8.3 - 5.4 4.5 G FeCl ₃ 0.015 5.5 14.9 11.7 - D. CuSO. 0.015 - 11, 2 - CuSO ₄ 0.015 13.6 12.1 6.9 - unconcerned
han-
del-t CuSO. - - ■ 15.0 30.1 23.4 26.5 -. · 28.8

As an anhydrous salt based on the weight of the wool.

209808/1897

- 33 -

Claims (1)

Claims . 1. Process for the modification of materials containing keratin by treating the material with (1) a resin that has at least two mercapto (thiol) groups per molecule and (a) the residue of a polyhydric alcohol, ("b) at least two poly- , - oxyalkylene chains connected to this residue, and (c) by oxygen atoms with carbon atoms of these ; Polyoxyalkylene chains connected at least two acyl radicals of a mercapto (thiol) group containing aliphatic carboxylic acid and / or at least two radicals of a mercapto (thiol) group-containing aliphatic Alcohol after removal of a hydroxyl group and; (2) a curing catalyst and curing the resin on the material, characterized in, that as a hardening catalyst either a salt - a heavy metal with a non-drying acid with an acid strength (-log pK) below 5 or a chelate a heavy metal (including the chelates, which are also salts) is used. 2. The method according to claim 1, characterized in that the Polythiol resin contains three to six mercapto groups in the molecule. 20 * 9808 / 18.97. 3 · * procedure according to. Claim 2, characterized in that the Polythiol resin has three or four mercapto groups in the molecule holds. 4 »Process according to claims 1 to 3» characterized in that the molecular weight of the polythiol resin is 400 to 10,000 amounts to. · 5. Process according to Claims 1 to 4, characterized in that that the polythiol resin of the general formula ■ £ 0-alkylene) _m OH ^ 0-alkylene) corresponds to where η, ρ and q mean positive integers, m is at least equal to 1 and in each of the total p and (q ~ 1) chains can have different values, η at most 2 and ρ is at least 2 and at most 6,
q is such a number that (p + q.) at least 3 and at most 7 is,. each of ^Il alkylene "groups a chain of at least 2 and at most 6 carbon atoms between successive oxygen atoms contains. ^ r- 2 09 808/1897 R is an aliphatic one having at least 2 carbon atoms Rest and X is an aliphatic containing at least one mercapto group Remainder "mean. · 6, 'method according to claim 5 »characterized in that the iPolythiol resin of the formula 40-alkylene) _m OH q-1 ■ (O-alkylene ) _m 0.CO. corresponds to where- R, "alkylene", m, ρ and q have the same meaning as in claim 5 and _Λ r represents a positive integer between 1 and 24 · Ί. Method according to claim 6, characterized in that the polythiol resin of the 3? 40-alkylene) _m OH q-1 40-alkylene) _m 0. CO. C ^ H ^ SH corresponds to where "alkylene", m and q have the same meaning as in claim 5 to have, - 36. 2119808/1897 ~ 36 - u is a positive integer of at most 2, P _{1 is} an integer of at least 3 and at most 6 and such a number that (p. + Q) at least 4 and at most 7 is, and R _{1 is} an aliphatic radical with at least 3 and at most Means carbon atoms. ' 8. The method according to claim 7 _5, characterized in that the 'polythiol resin of the formula. - • fO-alkylene) _m O.CO. corresponds to where ! 'alkylene "and m have the same meaning as in claim 5, u and p. have the same meaning as in claim 7 and Rg is an aliphatic radical with at least 3 and at most 6 Means carbon atoms. 9. The method according to claim 8, characterized in that the polythiol resin of the formula. CH O.CO.C _u H _2u SH GK - ^ - (0C _t H _2t ) _m O.CO.C _u H _2u SH CH, 0. CO. 209808/18 97 - 37 - CH ₂ ^CH: (00 _t H _{2t) m} O.CO.C _n H _2n SH (OH ₂ J ₂ CH CH, II O.CO.C _u H _2u SH corresponds to where m has the same meaning as in claim 5, u has the same meaning as in claim 7, and t is an integer of at least 2 and at most 3. 1o. Method according to claim 9 »characterized in that the Polythiol resin of the formula ₂ i ° ^C 3 ^H 6 ^ m ^0C0CH 2 ^SH OCOCH ₂ SH * 2 (OC ₃ H ₆ ;) OCOCH ₂ SH corresponds to, where . m has the same meaning as in claim 5 and the polythiol resin has a molecular weight in the range of 1,000 to 5,000. 11. The method according to claims 1 to 5, characterized in, that the polythiol resin of the formula 40-alkylene) _m OH ■ 1 Jq-1 40-alkylene) 209808/1897 - 38 - corresponds to v / ob ei R ₅ -OH, - (0-alkylene) _v 0H, -0.CO.C _u H _2u SH or - (0-alkylene) _v O.CO.C _u H _2u SH, R, "alkylene", m, ρ and q have the same meaning as in claim 5 have u has the same meaning as in claim 7 and ν is an integer of at least 1 included in each of the p-chains can have different values. 12. The method according to claim 11, characterized in that the polythiol resin also of the formula 40-alkylene) _m OH q-1 40-alkylene) corresponds to where "alkylene ¹¹ and m have the same meaning as in claim 5, R ₁ , p. and q have the same meaning as in claim 7 and R has the same meaning as in claim 11. Method according to claim 12, characterized in that the polythiol resin also the formula 40-alkylene) _m corresponds to where - 39 - 209808/1897 Rp has the same meaning as in claim 8, P _{1 has} the same meaning as in claim 7, "alkylene" and m has the same meaning as in claim 5 and R., the same meaning as in claim 11. 14. "The method according to claim 13» characterized in that the polythiol resin-also of the formula '..-- .; Rr OCH ₂ CHGH ₂ SH OH corresponds to where m has the same meaning as in claim 5 _f t the same meaning as in claim 9 »P _{1 has} the same meaning as in claim 7 and Rp has the same meaning as in claim 8. 15. The method according to claim 13 »characterized in that the polythiol resin also of the formula OCH ₀ CHCH ₀ SH (QC _t H _2t ) _v OH corresponds to where R _{2 has} the same meaning as in claim 8, m the same meaning as in claim 5, ■ p- the same meaning as in claim 7 »t the same meaning as in claim 9 and 209808/189 7 - 4ο - ν has the same meaning as in claim 11. 16. The method according to claim 14, characterized in that • the polythiol resin also of the formula CH ₂ (° ^C 3 ^H 6 ^ m ^OCH 2 ^CHCH 2 ^SH OH- CH ( ⁰ S ¹ Vm ^0CH 2 ^CHCH 2 ^SH • OH ₅ Hg) _1n OCH ₂ CHCH ₂ SH OH corresponds to where m has the same meaning as in claim 5 and the polythiol resin has a molecular weight in the range of 700 to 3,500. 17. Process according to Claims 1 to 16, characterized in that the catalyst is a salt or a chelate of a metal from groups IB, HB, IVB ₉ VB, VIB, VIIB or VIII of the periodic table. 18 .. The method according to claim 17, characterized in that the catalyst is a salt or a chelate of titanium, vanadium, Chromium, manganese or nickel. 19. The method according to claim 17, characterized in that the Catalyst is a salt or a chelate of iron, cobalt or copper. '· 209808/1897 20. The method according to claims 1 to 19, characterized in that that the catalyst is a salt of a mineral acid. 21. The method according to * claim 20, - characterized in that the mineral acids hydrochloric acid, hydrobromic acid ^ Nitric acid j sulfuric acid, phosphoric acid or phosphorous Acid is. 22. The method according to claims 1 Ms 19 »characterized in that that the catalyst is an organic acid salt. 23. The method according to claim 22, characterized in that the organic acid is chloroacetic acid,! Fumaric acid, maleic acid, Is oxalic acid, salicylic acid, or citric acid. 24. The method according to claims 1 to 19 »characterized in that that the catalyst is a chelate of a compound in which the chelating atoms are oxygen and / or nitrogen are. 25. ' Method according to claim 24, characterized in that the Chelating compound a 1,2-diketone, a 1,3-diketone, is an alkylenediamine or ethylenediaminetetraacetic acid. 26. The method according to claims 1 to 25, characterized in that the catalyst in an amount of 0.01 to 10 wt. ^, based on the weight of the polythiol resin is used. 209808/1897 - 42 - 2,38448 27. The method according to claim 26, characterized in that the catalyst in an amount of 0.1 to 5 wt. $, based based on the weight of the polythiol resin. 28. The method according to claims 1 to 27, characterized in that 0.5 "to" 15 wt. $ Of the polythiol resin, based on the Weight of the treated keratin-containing material. will wear. . ■ 29. The method according to claims 1 to 28, characterized in that that the treated keratin-containing material is heated to an elevated temperature to harden the polythiol resin, 30. The method according to claim 29, characterized in that the keratin-containing material is heated to a temperature in the range from 40 to 180 ° C. 31. The method according to claims 1 to 30, characterized in that the polythiol resin in the form of a solution in an organic Solvent or in the form of an aqueous dispersion or emulsion is applied. 32. The method according to claim 31, characterized in that the polythiol resin in form of a solution in a chlorinated and / or fluorinated hydrocarbon; stofed with no more than 3 carbon atoms is applied. - 43 209808/1897 33. Process for the shrink-proof finishing of keratin-containing Materials, characterized in that the keratin-containing Material a polythiol resin according to claims 1 to 16 and a catalyst according to claims 1 and 17 to 25 . wearing. 34. The method according to claims 1 to 33 »characterized in that that the keratin-containing material is solid fibers or a fabric made from them. 35. Process for the non-iron finishing of materials containing keratin in the form of piece goods, characterized in that one the piece goods ■ - (1) with a polythiol resin according to any one of claims 1 to 16 and a catalyst according to any one of claims T and 17 to 25 treated, (2) processed into an item of clothing or a part thereof and (3) brings it into the desired shape. 36. Process for the non-iron finishing of materials containing keratin in the form of piece goods, characterized in that one is on a garment already brought into the desired shape or a part thereof, a polythiol resin according to any one of claims 1 to 16 and a catalyst according to any one of claims 1 and 17 to 25 applies. f, 209808/1897. ■ - 44 - 44 -. 37. The method according to claim 35 or 36, characterized in that the item of clothing or the part thereof is brought into the desired porin by treating with a setting agent ("setting agent"), keeping the treated area in the "desired shape and heat and pressure exercises on this. 38. Method for smoothing ("flat-setting") and for the shrink-proof finishing of keratin-containing piece goods, thus identifiable "indicates that the piece goods are treated with a setting agent (" setting agent ") by heating in the moist state fixed flat, then with a polythiol resin according to one of claims 1 Isis 16 and a catalyst according to one of claims 1 and 17 to 25 impregnates and dries and then the polythiol resin cures. 39. The method according to claims 35 to 38, characterized in that the keratin-containing material is a wool fabric or one thereof manufactured garment. 4Ö. Kerätinhaltiges material, characterized in that it has on its surface a polythiol resin according to any one of claims 1 to 16, which in the presence of a catalyst cured according to one of claims 1 and 17 "to 25 became. 209808/1897 41. Keratin-containing material, characterized in that it has a polythiol resin according to one of the claims on its surface 1 to 16 in a still hardenable state and a catalyst geinäß one of claims 1 and 17 to 25 has. 200808/1897