DE1934678C3 - Process for modifying fiber materials containing keratin - Google Patents

Description

a) a residue of a polyalcohol,

b) at least two polyoxyalkylene chains bound to this radical and

c) at least two through oxygen atoms to carbon atoms of the polyoxyalkylene chains bonded residues of the carboxylic acids containing mercapto groups from (1) acyl residues and (2) residues of mercapto groups that result after removal of a hydroxyl group, belong to groups formed by apphatic alcohols,

and whose molecular weight is 400 to 10,000 and the mercapto compound fixed to the keratinous material.

2. The method according to claim 1, characterized in that the mercapto compound 3 to 6 mercapto groups contains in the molecule.

3. A method according to claim 1, characterized marked ■, characterized in that the mercapto compound of the formula

CH ₂ - <- O - C ₃ H ₆₎ - O - CC) -CH ₂ -SH, CH (-O - C ₃ H _b) ~ O - CO - CH ₂ - CH ₂ SH -i- O - C ₃ H _n ) - O - CO - CH, - SH

corresponds to, where m is an integer of at least 1 value.

4. The method according to claim 1, characterized in that the mercapto compound of the formula Materials at pH 7.5 to 12 are treated with the mercapto compounds.

8. The method according to any one of claims 1 to 7, characterized in that the keratin-containing Material for fixing the mercapto compounds is heated to 30 to 180 C.

9. The method according to any one of claims 1 to 8, characterized in that the material treated with the mercapto compounds, made articles of clothing from them or parts thereof and apply folds to these in the desired places.

10. The method according to claim 9, characterized in that the folds are attached by you treat the material with a fixative, fold it, and heat and mechanical Applying pressure to it.

C- H ₂ -K) - C ₃ H ₆ ) - O - CH ₂ - CH - - CH ₂ - SH

OH

-I- CH O - C H _{3 ft)} - O - CH ₂ - CH - CH ₂ - SH

OH

CH ₂ IO- C ₃ 1-1 ,,) "; - O - CH ₂ - CH - CH ₂ - SH

OH

4: S.

5: s

corresponds to, where m is an integer of at least 1 value.

5. The method according to any one of claims 1 to 4, characterized in that the amount of mercapto compound, based on the treated. keratinous material, 0.5 to 15%.

6. The method according to any one of claims 1 to 5, characterized in that catalysts for the fixation of the mercaplo compound in amounts of 0.1 to 20%. bc / ogen on the Mcrcaptoverbin- (, ^ dung, can also be used.

7. The method according to any one of claims 1 to 6, characterized in that the keratin-containing From French patent specification 15 14 843 a method for treating keratin fibers, in particular a method for making permanent folds in keratin-containing textile fiber material using simple thiols and disulfides are known.

These thiols and disulfides differ fundamentally from those used according to the invention Mercapto compounds. According to FR-PS 15 14 843 thiols such as thioglycerol, thioglycolic acid. Thiolactic acid, Thioglycolate of ethylene glycol or glycerine, / i-mercaptoethanol and N-carboxymethylmercaptoacetamide used, and the disulfides of these thiols are used as disulfides. It deals So they are all about low molecular weight, simple sulfur compounds, and there are always two different sulfur compounds are used together, namely a thiol and a disulfide.

According to the invention, however, higher molecular weight polymercapto compounds are now used, in which an the remainder of a polyalcohol via at least two polyoxyalkylene chains bound to this remainder an alcohol containing mercapto groups or a carboxylic acid containing mercapto groups are bound, the mercapto groups are in their final position. No disulfides are used.

The sulfur compounds of FR-PS 15 14 843 and those according to the present invention have little or nothing in common and can hardly be compared with one another. The ones used according to the invention Polymercapto compounds mediate the treated, keratin-containing fiber material at the same time permanent shapes and a permanent shrink-proof finish. With the connections of the citation however, it can only provide permanent deformation and no useful shrink-proof finish can be obtained. These advantageous results which are achieved according to the invention are completely surprising and unexpected.

The present invention relates to a process for refining keratin-containing fiber materials! especially to Schrurnpffeäirnaciien and for permanent deformation.

Individual methods for making keratin fibers shrink-proof are known, including resinous ones

u-imuen can be applied to piece goods or those of other processing levels. By yes. ' ^e i ^{rar L} "fl><; armament processes are the prostitute! chrumpfTcsUusruM j shrinkage

^ionCn S iSSriii ^

! chrp

^ionCn S «
, erursau

^{at the}
(so-called

_Ver r _a h _rcn to permanent deformation "

R including the rental here G. woru, ^

Tcxtiltrtikcls are retained durable press equipment). and partly become here against residues of mereapto-group-containing aliphatic alcohols belong to a formed group,

and whose molecular weight is 400 b ^ K) WX) beirägl and the riveted connection on the kerat.nhakigen Material fixed.

Both in shrinkage and in the ^ ^^. ^ _{WwJen after the} previous

drive equipments that be. _m washing ".n the washing machine on its original Dimens and retain shape. In addition to the excellent grill

of the material treated according to the invention "£ l

Application _f e ^ neter middle, like water. Re-

Equipment a strong movement in warm up Ä Withstand water containing detergent, ei form-proof and shrink-proof equipment

BiBSBi material /. B. ^Κ
appropriate scm D
Exclusively ^you

Adorable material can or from mixtures ^ or

much

- and

Jitodunecn mitendsUndigen MTCapmgruppen «

by ₈ c. _i8 n _e , e

Kvon solutions in organic solutions or treated by aqueous en.uls.oncn, which

a, a residue of a polya.koho.s,

b) at least two Poh oxyalkylene chains bound to this radical and

c, "iid at least two by OxygenTaUHnean Kohödesten" equals 1 and in

_{V () rhaildcncn lp +} , .. 1, ^ «» ^^

^ ¹ ■ ^ TnAsVeS ^ ÄÄ 7, st.

^ fcn / wipe successive stay in acid. R an al.phatic. mt ^ at least

to see rest means

The —Ο — alkylene groups in the individual poles oxyalkylene groups can be different from one another and, if appropriate, substituents such as phenyl or contain chloromethyl groups.

So you can especially esters of the formula

[(-O-Alkylcnj-OH] ,.

[(—Ο— alkylene) - O (O (/,.1I ₂ , - SII] ,,

use where R, "alkylene". hi, ρ and q have the meaning given and r is a whole positive number, e.g. B. represents a value of at most IS or even 24th. '>

Here are the esters of the formula

H-O-alkylene), - OH], _,

HO- alkylene) - O-CO - C ₁₁ H ₂₁₁ --SH] _n ^"ü

preferred, in which "alkylene", m and q have the meaning given, u is a positive integer with a value of at most 2 and p, an integer with a value of: s represents at least 2 and at most 6, (/>, + q) is at least 3 and at most 7 and R _{1 is} an aliphatic radical having at least 2 and at most 6 carbon atoms.

Esters of the formula w are also preferred

[R ₂ ] HO-alkylene-R ₂ ) -0-CO-C "H _2II -SH] _; , _:

(4)

35

where "alkylene", hi and u have the meaning given, p _{2 is} an integer of at least 3 and at most 6 and R is an aliphatic hydrocarbon radical with at least 3 and at most 6 carbon atoms.

Finally, especially those are different from glycerin. Hexane-1,2,5- or -1,2,6-IrioI and ethylene oxide and or or propylene oxide derived ester, d. H. those of the formulas

CH ₂ - (OC ₁ H ₂₁ ) -0-CO-C ₁₁ H ₂₁₁ -SH

CH- (OC ₁ H ₂₁ Js-O-CO- C ₁₁ II ₂₁₁ -SH
CH ₂ - (OC, H ₂ ,) - O - CO - C ₁₁ H ₂ "- SH
and

CH ₂ - (OC ₁ H ₂₁ ) SO-CO-C ₁₁ H ₂₁₁ -SH
CH- (OC ₁ H ₂₁ JO -CO-C "H _2u -SH
CH ₂
CH,

(5)

CH ₂ -

[- (OC ₁ H ₂ ,) ,, - t) - (l)

SiT

preferred, in which hi and u have the meaning given and t is an integer of at least 2 and at most 3.

The poly-uxyaikylenmercapto-cster to be used according to the method can be prepared by adding polyalcohols, ammonia, or amines mil Reacts alkylene oxides and the resulting polyhydroxypoly-oxyalkylene compounds esterified on at least two hydroxyl groups with mercaptocarboxylic acids.

As polyalcohols, for. B. Consider: Ethylendycol. Poly (oxyethylene) glycole, propylene glycol. Poly (oxypropylene) glycols, propane 1,3-diol, poly (cpichlorhydrine), Butane-1,2-, -1,3-, -1,4- or 2,3-diol. Polv- (oxy-1,1-dimethylethylene glycols, poly (tetrahydrofurans). Glycerine, 1,1,1-trimethylolethane, 1,1,1-trimethyloipropane, Hexane-1,2,5- or -1,2,6-triol. Pentaerythritol, dipentaerythritol, mannitol, sorbitol. Investment products made from alkylene oxides and ammonia or amines such as diethanolamine or tetrakis (2-hydroxyethyl) ethy] endiamine; the nitrogen compounds mentioned are first converted into polyalcohols by the alkylene oxide.

The alkylene oxides are ethylene oxide and propylene oxide. also butylene oxides, epichlorohydrin and tetrahydrofuran mentioned. If desired, the polyalcohol can Treated with a certain alkylene oxide like propylene oxide and then the chains with another Alkylene oxide such as ethylene oxide can be lengthened somewhat.

The mercaptocarboxylic acids used for the esterification are thioglycolic acid (2-mercaptoacetic acid) and 2-mereaptopropionic acid preferred. However, other mercaptocarboxylic acids such as mercaptoundecanoic acid can also be used and mercaptostearic acid can be used

The mercaptoesters primarily suitable for the present process are those which are obtained from glycerine, propylene oxide and thioglycolic acid and hence the form

CH ₂ -IOC ₃ HJ-O-CO-CH ₂ -SH

CH -i- O- C ₃ H ₆ ) SO-CO-CH ₂ - SH (7)

CH ₂ -VOC ₃ HJ-O-CO-CH ₂ -SH

correspond, where m has the meaning given. Their molecular weight is advantageously between 10 (X and 5000. Such compounds are known.

As already seen from the general definition borrowed, can not nui in the present proceedings Mercaptoester, but also Mercaptoälher are used del such. B. those of the formula

[- (O-alkylene) -OH], _, - (O-alkylene) -0-CH ₂ -CH-CH ₂ -SH

where R, "alkylene", m, ρ and q have the meaning given and R _{3 is} one of the groups —OH

Oo - (O — alkylene), .— OH, —O —CO — C ₁₁ H ₂₁₁ -Sl · and - (O — alkylene) ,, - O — CO —C “H _2u —SH, where 1 / has the meaning given and r stands for a whole positive number, which can take on different values in each of the /> Kcttei. The oxyalkylene

(> s groups in the individual polyoxyalkylene chains can also be different here, but preferably di> the same and otherwise, if desired, substituted being. z. B. by phenyl or chloromethyl groups

The ethers of the formula are preferred here

[(—O —Alkylcn ^ -OH], ..,
R ₁ (9)

'(-O-alkylene) ^ - U-CH ₂ -CH-CH ₂ -SH'

R,

where "alkylene". Ri, R ₃ , m, p, and q have the stated ι ο meaning, and also those of the formula

(-O-Alkylcn) -0-CH ₂ -CH-CH ₂ -SH
R3

The ethers of the formula are very particularly preferred

CH ₂ - (O -C ₁ H ₆ ) -0-CH ₂ -CH-CH ₂ -SH

OH
CH- (O-CH ₆ ) SO-CH ₂ -C ¹ H-CH ₂ -SH

OH
CH ₂ - (OC _-1 H ₆ ) AT-O-CH ₂ -CH-CH ₂ -Sh

OH

(13)

(10) (in which the values;? Ι of the individual chains are different

can be) whose molecular weight 700 to 3500

in which R ₂ and p _{2 also have} the meaning given.

have, but especially the ethers of the formula The ether-ester compounds of the formula 8, in which

R _{3 is} a remainder of the composition

HOC ₁ H ₂₁ ) SO-CH ₂ -CH-CH ₂ -SH '

O-CO-C ₁₁ H ₂₁ -SH

OH

II)

.15

wherein R ₂ , /, m and p _{2 have} the meaning given and of which individual are known.

The ethers of formula 8 can be prepared by methods known per se. Those which _{contain a hydroxyl group as R 1} are obtained by adding alkylene oxide to a polyalcohol, etherifying the hydroxyl groups of the adduct with epichlorohydrin and replacing the chlorine atoms with mercapto groups using sodium hydrogen sulfide (see US Pat. No. 32 58 495 and British Patents 10 76 725 and 11 44 761). In many cases the average number 4c of mercapto groups per molecule is not an integer; it can be 2.6, for example. This is partly due to the fact that the chlorine atoms are not completely replaced by mercapto groups and is partly due to side reactions. So z. B. the chlorohydrin ether formed in the reaction with epichlorohydrin wcitcrrcagiercn with epichlorohydrin and thereby a product can be formed which has two replaceable chloralomc on a hydroxyl group originally present in the polyalcohol. so

Another group of preferred ethers are those of the formula

or one of the composition

- (O-alkylene) -0-CO-C ₁₁ H ₂₁ -SH

means, can by esterification of the corresponding alcohols with mercaptocarboxylic acids of the formula

HO-CO-

-C ₁₁ H ₂₁₁ -SH

C ₁ Il

,) ,,, 0-CH ₂ -CH-CH ₂ -SH

wherein R ₂ , I, in, ν and /> _{2 have} the meaning given.

Ethers of the formula H, in which R _-1 denotes a Ciruppe of the composition (O alkylene), OH, can be prepared by converting polyhydric alcohol. Alkylene oxide and Hpichlorohydrin Crhiillcnc products first react again with an alkylene oxide and then with sodium hydrogen sulfide la IW (see Biiti see patent specification Il 44 761).

can be obtained.

In the present process, the mercapto compounds on its own or together with other means, e.g. B. resins or resin formers, such as Aminoplasts, or particularly epoxy resins (i.e. compounds that on average have more than one 1.2-Epoxygruppc contained in the molecule) can be used. Particularly good results can be obtained are made with mixtures of polymer captive compounds and prepolymers of polymeric polyhydroxy compounds and polyisocyanates. Examples of this are prepolymers made from polyoxyalkylene glycols and aromatic diisocyanates or from poly (oxyalkyl) triols and aliphatic diisocyanates! mentioned. In particular, here is the combination of the polymer-captive compound A (for more details, see below below) and due to the content of free, aliphatic isocyanate groups to form a polyurethane to mention capable products on the fiber.

Many of these polymeric aptovei bonds are in Insoluble in water, but can be used in an aqueous dispersion or emulsion. Preferably However, the PolymercaptoverbiiHlimgen ais solutions in organic solvents applied to the fiber material, e.g. H. as a solution in low Alkanols such as ethanol, lower ketones such as ethyl methyl ketone, benzene, halogenated hydrocarbons. in particular chlorine and / or l'luorilkaiien or alkylenes, which have at most three carbon isloflatonia contain, such as dry cleaning agents: carbon tetrachloride. Tiichloiethylene. Pci chloral hylen

The amount of Polymercaplovci binding is determined

ίο

padded. Finished or semi-finished items will be appropriately sprayed, or, even more advantageously, an organic containing the polymercaptan Circulating solvent. Dry cleaning agents and dry cleaning agents are particularly suitable for this purpose.

^aP to ^d S ^e chrumpffestausiüstung are the poly mercapto compounds usually piece goods on aulaebracht, though. as already stated, also ate, application to the top is possible. Before or after the treatment with the polymercaptans, piece goods can be smoothed ("flat-setting"), but it should be noted that this can be unnecessary or even impractical for certain types of tissue. Smoothing is usually done by treating the fabric with steam or in the presence of a smoothing agent and moisture with steam or atmospheric pressure, whereby it is kept wide - the same effect can also be achieved by using a reducing agent in high concentration and a swelling agent and then Washing out the excess of these agents while keeping the muck wide can be achieved. Another method is to use a swelling agent on the material

depending on the type of effect desired. In most cases, amounts of 0.5 to 15% are suitable. calculated on the material to be treated, hur one Stabilization of knitted or knitted fabrics usually requires 1 to 10% mercapto compound A high level of shrinkage resistance can be found on webware and form hardening as well as a substantial crease resistance with rather smaller amounts, 1 up to 5% can be achieved. The feel of the goods naturally also depends on the amount of polymercapto compound away. The necessary to achieve the desired effect can be obtained by simple preliminary tests Easily determine the minimum quantity. The structure of the tissue can also influence this minimum amount

to have. , "~.

Only then does the desired effect fully occur when practically all of the amount of polymercapto compound present on the material is fixed At room temperature, this can take 5 to 10 days or more. However, the fixation can are substantially accelerated with the aid of catalysts. Preferably, the catalyst is simultaneously with the polymercapto compound towards the

material to be treated applied, if desired ".v · .. ^ ....- —... ...

but this can also be done before or after. _i5 and an alkanolamine carbonate, ζ B. H _; never toe for the fixation depends on the type of ethanolamine carbonate, impregnated, get.ocknet and catalyst and accordingly one chooses decatated with wet steam. _Pn | _vme r-

? en KaStator depending on the requirements that can form fixed equipment m. de. P ^

when applying the procedure in detail captanen received in different ways who As Kaial / satoren z. B. Organic 30 One of them is that you can do the MjgaW or inorganic bases, so-called siccatives, oxy- dem Polymercaptan treated therefrom Fe w

or anorganic _ _v fe. _; „_ _{J: i} _, ^,, manufactures semi-finished articles and then the desired

Applying wrinkles using reducing agents, bases or superheated steam. The 1 oi> mercaptan can be applied to any Hersie. management level are used, z. B. the top, the yarn or the piece goods. Gewünschtentalis can mercapto wool ^bloc J ^{ie, reindeer} _at

lenediamine diethylenetriamine, 1 nainyienieiramm, ie- means such as formaldehyde or higher aldehydes TraäthXn'pentamin and Hexamethylenediamine give the deformed articles after the fixation of the pole mentions The water mercaptans can be used as organic bases. ,, "" üstune

ms chen oxides and hydroxides, z. B. A Preferred Method of Formfcstdusrustunfc

Sodium hydroxide or ammonia. Examples of is, which is already wrinkled, c. Sikkuve are calcium, copper, iron, lead, cerium, or semi-finished articles with naphthenate in organic solution and cobalt naphthenate. Examples of hydroxide and medium-dissolved polymercaptans of the hydroperoxides are cumene peroxide and tertiary butyl anhydride 7.11 heh: mdcln. The application in 1 hydropcroxyd, Dicumylperoxid, Dilaurylpcroxyd,
Methyl ethyl ketone hydroxide, diisopropyl hydroxydicarbonate and chlorobenzoyl hydroxide.

The fiber materials are preferably at pH < Values above 7, appropriately those from 7.5 to 12, are treated; under acidic conditions requires the Fixation generally longer period.

The amount of Kalalysatoren can vary within wide limits, "in general you need 0.1 to 20%, preferably 1 to 10% catalyst, based on the weight of the fiber; but it can also be essential higher amounts are used '.

The fixation of the mercapto compounds can be promoted by higher temperatures in order to! The tempei-itur lies for a particularly quick fixation between 30 and IK (VC. libcnso, high humidity can cause fixation in the presence of catalysts accelerate.

The l'polymercaplanc and, gogebcnenliills. also the Kiiilysatiiien can in the usual way aiii that l'isei material has been applied. Wollkamnv / ΐιμ For example, piece goods are dipped or

or inorganic around ''. o ^ w ......... "." "_...-, _ ..,

dative curing agents or free radical catalysts such as azodiisobutyronitrile, peroxyde, hydroperoxides can be used individually or in combination with one another.

Among the organic bases are primary or secondary amines e.g. B. lower alkanolamines such as mono- and diethanolamine, and polyamines such as ethylenediamine, Treat diethylenetriamine, triethylenetetramine, Te-Art. The application in orgar Solvent is essential here, because in the medium the traps wind away again.

According to another method, which largely relates to the granting of dimensional stability, ci.i. Piece only where it is to be folded, with n «-" Impregnated with polymer caplan and then under Aiuvl Application of heat and pressure after application and folds kept in shape. . . · ,.

Smoothing or Ureilhallen. indifferent · or> ciil. happens before or after the treatment with the ^lol > ^mi 'captan, can be carried out according to any, ^b f J ¹ ' ¹¹¹¹ ^ methods, / .. B. nut reduction, averaging, bases. Water or superheated DainP monoethanolamine sesquisuin. is the most iy used remedy. Us can be used together with a UW- ' mittet such as urea.

In all of the preceding and following Ai ningen mean the parts Gcwichlsteile and you / cute weight percentages.

For now, some of the Rire Hrlinduni- ¹ will now be described w Liehe Prümielhoilcn and anschlu'iH 'H follow Herstcllungsvorsclmflcn for l'olymcivaptaiK

, en I-

Test methods
Standard laundry

Before testing for surface softness and wrinkle resistance, unless otherwise stated, all samples for one hour in a household drum washing machine in a phosphate-buffered one Washed liquor with a pH of 7 at 40 C in a liquor ratio of 1:22. After removal from the washing liquor and spinning off in a laundry centrifuge, the patterns become violent three times shaken and then hung to dry at room temperature, if possible in a vertical position Position of the folds.

Shrink

The difference in the measured quantities is used as the shrinkage of the piece measured before and after washing. The area shrinkage is derived from the linear Calculated shrinkage.

Dryness index
(»Smooth-Drying-Index«)

The surface softness of the article to be tested after the standard wash is determined by comparison with

the three-dimensional, plastic Monsanto »Washn-Wear« Scale determined. This consists of a series of 5 graduated plastic strips with different, Surface texture characteristics on a scale from 1 to 5. The test objects are illuminated at an angle of incidence of 16 °. The same thing always happens with a Monsanto strip. and by comparison with these, the degree of surface softness is found. Grade 5 means one ίο Very little or no change in appearance after washing.

Wrinkle fixation degree

The durability of the folds in the standard laundry is compared to that published in the Journal of the Textile Institute 53, S. 143 (1962) described device measured: The folded piece is in the center of rotation of a Brought a slit-shaped light source, the axis of rotation is at right angles to the FaIt and the slit of light is parallel to. The light source is rotated until the shadow of the fold just disappears, and the angle of incidence of light measured. Then the light source is rotated again until the shadow disappears from the the other side and again the angle measured. The 2s strength of the wrinkle fixation is then calculated as

Percentage fixicrunn = mean angle of incidence
______

100.

Accordingly, the stronger the measured wrinkle, the higher the value of the degree of fixation.

Manufacturing regulations
Polymercaptan A

A mixture of 800 g (0.2 mol) of an adduct of average molecular weight 4 (XX) from glycerine and propylene oxide, 55.2 g (0.6 mol) Thioglycolic acid, 5 g of toluene-p-sulfonic acid and 350 g Toluene are heated to reflux temperature under a nitrogen atmosphere. After 10.8 ml (0.6 mol) Water of reaction have been removed azeotropically, the mixture is cooled, washed with water and separated the organic layer. After removing the solvent by vacuum distillation this leaves 793 g (94% of theory) of the desired trimcrcaplan (polymercaptan A), the molecular weight of which is equivalent to its molecular group per kg is 0.59.

Polymcrcaptans B and C

It is poly (2-hydioxy-3-mcrcaplopropyl) -äthcr, those from glycerine propylene oxide investment products with a molecular weight of 600 (B) or 4KlX) (C), epichlorohydrin and sodium sulfide will. The mercapto group score of compound B lies 3.7, that of compound C 0.32 equivalents per kg.

Polymercaptan. · D to S

These are specified in A according to that for Polymercapt Regulation established, but with the following changes: In the case of the Polymereaptanen .1 to S becomes iinstcllc of toluene, Pcrrhlorälhylcn used. at D to 1, the Rc.iklionsgemis.li is not mixed with water washed; Any unreacted mcrcurbonic acid still present is combined with the organic Solvent by treatment in one Red totalion vacuum evaporator removed. Polymercaptan P is produced without a catalyst.

The starting materials used for the production of these polymercaptoesters are shown in Table I to ent-.15 to take.

Polymcrcaptans T and U

These are poly (2-hydroxy-3-mercaptopropyl) ethers. similar to B and C. Polymercaptan T contains 2 to 3 HS groups per molecule, its mercapto group content is 1.4 equivalents per kg, its average molecular weight lies between 1500 and 2000. Mercapto compound U contains about 3 HS groups per molecule, their mcrcapto group content

-15 is 0.54 equivalents per kg and their average Molecular weight about 3000 (compare formula 8).

Polymercaptan V

5 <i A mixture of 5 (X) g Polymercaptan B, 218 μ (2.37 equivalents) thioglycolic acid. 1.5 g of toluene-psulfonic acid and 500 ml of Perchloräthylcn is 8 hours heated for a long time under a nitrogen atmosphere and under reflux and the reaction water continuously

ss removed. It is then washed with water until the washing water has a pH value between 5 and (1 , and the organic solvent is then distilled off in vacuo. The residue has a methyl group of 5.7 equivalents per kg and

ι «, contains 5 to f> HS- (ii uppcn in the molecule.

i'olvmcreaptan W

A mixture of 529 g of polymer ^{caplet in C. I 1} g (0.212 equivalents) of thioglycolic acid, 1 g of toluene-p- (ssilfonsiuiie and 350 ml of perchlorethylene is heated as indicated, with 4 ml of water being distilled off. The mixture is then with a porridge us 5 ν Niitriumhydrogcnciirbonal and 2.5 ml water vet

stirs, filtered off and vacuum distilled. The residue (532 g) has a mercapto group content of 0.58 equivalents per kg or 5 to 6 mercapto groups per molecule.

Poly mercaptan X

Is made in the manner described in Door V from 500 g of Polymercaptan T, 89 g of thioglycolic acid, 4 g of toluene-sulfonic acid and 500 ml of perchlorethylene produced.

with elimination of 23 ml of water. The mercapto group content of the residue is 1.78 equivalents per kg or 5 to 6 groups in the molecule.

Polymercaptan Y

Is made from Polyrnercaptan U and 36.4 g thioglycolic acid, but otherwise made like X. The residue has a mercapto group content of 0.75 ίο equivalents per kg and 5 to 6 groups per molecule.

Table 1

Bczcichm ing alkyl oxide additive product made of Alcohol or amine Esterified with Average Glycerin molckulargewiclil Alkylenoxyci Glycerin Propylene oxide D. 3000 Propylene oxide Glycerin Thioglycolic acid E. 5000 thereupon a little ethylene oxide Glycerin Thioglycolic acid Propylene oxide Glycerin F. 1000 Propylene oxide Thioglycolic acid G 3000 H) ⁰ O ethylene oxide Glycerin Thioglycolic acid H 3000-4000 90% propylene oxide Thioglycolic acid Propylene oxide Glycerin I. 1000 2-Mcrcapto Propylene oxide Glycerin propionic acid J 5000 thereupon a little ethylene oxide Glycerin Thioglycolic acid Propylene oxide Glycerin K 1000 Propylene oxide Hexane-1,2,6-iriol Thioglycolic acid L. 700 Propylene oxide Glycerin Thioglycolic acid M. 3000 Propylene oxide Thioglycolic acid N 1500 Propylene oxide Ethylenediamine Thioglycolic acid O 4000 Pentaerythritol 2-mercapto- Propylene oxide Triniethylol propane propionic acid P. 500 Propylene oxide Butane-1,4-diol Thioglycolic acid Q 2220 Propylene oxide Thioglycolic acid R. 4040 Tetrahydrofuran Thioglycolic acid S. 1000 Thioglycolic acid

Example I.

Solutions with 2, 5 and 8% polymercaptan Λ in chlorinated metal are prepared. With these Knitting patterns made of Zephyr wool yarn are impregnated on the foulard with 100% absorption and solutions then dried at 50 ° C. After 12 days of storage at room temperature, the musler are placed in the Washing machine for 30 minutes in the event of a fleet change 1:25 and then the percentage area shrinkage is measured, mil following results:

In the much more stringent test, in which the flotation ratio is 1: 12.5 and the duration is 60 minutes the results are as follows:

IVilvmcrcapUti A% lliu-liciisdinimpfunp

3 0

% l'olynicaaplan Λ% ΙΠιγΙημι-, ι ΙιπιιιιρΓιιιΐ} ·

40 3 0 0

This shows the dependence of the action on ilei Amount of polymeicaptan. The excellent Schnmiplicslif'keii will echo without the soft one the handle of the knitting wool is affected. Also hai has shown itself to educate them in this way. Equipment against TnKkcnieinijMingsmitlel and Mehrfachwiische in wäll rigen Wascliinillellösiinucn is wklmlaiulslahig.

Example 2

20 g of Polymereaptan B are dissolved in 300 ml of trichlorethylene solved. In 363 ml of trichlorethylene 10 g a diglyeidylether of 2,2-bis- (4-hydmxyphenyl) -> propaps with an epoxy group content of 5.2 equivalents solved per kg. The two solutions are combined and the resulting mixture is used Knitwear of the type specified in Example 1 to 143% liquor pick-up poulardierl. After the dry i < > Newly at 50 C, the goods are left at room temperature for 24 hours and then in the Machine for 30 minutes at a flotia ratio washed by 1:25. The is treated with 4.3% of the agents mentioned in this way shrinks here Material does not fit in at all, while untreated goods show a shrinkage of around 40%.

B e i s ρ i e 1 3

A piece of gray worsted flannel is treated in a dry cleaning machine with a solution of the polymercaptan A in perchlorethylene for 5 minutes and then spun such that the weight gain is about 30%, and v _{5 is} thus about 3% Polymereaptan be located on the fiber material. After drying, the material is stored for 10 days at 20 ° C. and 85% relative humidity and then made into a garment. This is then brought into the desired shape under steam of 1.4 kg · cm " ² for 10 minutes. Finally, it is washed for one hour under normal conditions and, after being spun off, dried a fixation of 83% and a dryness index of 4 to 5. With the same wash, the corresponding untreated material becomes matted and the pressed-in folds have disappeared.

Example 4

A piece of gray worsted wool sergc is smoothed by padding an aqueous solution of mono-ethanolamine sesquisulfite containing 0.1% of a wetting agent, the absorption being 2% sesquisulfite and 60% water. The product is then treated in a rolled up state for 5 minutes with steam under atmospheric pressure and _so _ finally dried tension-free. Now the fabric is made into trousers and the creases are prepared by spraying a 5% solution of monoethanolamine sesquisulfite in the area of the creases so that about 2% sesquisulfite and 40% water, based on the weight of the fabric, are absorbed there . The trousers are then treated in a Hoffmann press, first for 20 seconds with steam and pressing, then for 20 seconds without steam, and (, o then under vacuum until they cool down without pressing a solution of Polymereaptan Λ which still contains 2% (calculated on Poly met capiaii A 1 diethyl triamine, treated in such a way that it finally contains 2.5% of its own weight of Polymereaptan. After six days, the trousers are subjected to the standard wash , and it keeps its hanger traps excellently at the same time.

Example 5

A piece of wool with a checkered pattern is impregnated on a padder with monoethanolamine sesquisulfh solution in such a way that the sesquisulfii absorbs 3% of its own weight. The fabric is dried practically tension-free on the stenter and cut to size for the production of a pleated piece of clothing (pleated jupe). The pieces are sprayed with water up to a weight increase of 30%, placed in folds between paper molds and these are ^{fixed by steaming in the autoclave 1} for 10 minutes at a steam pressure of 0.56 kg · cm " ^2. After drying and removal of the The garment is made into a paper former and treated with Polymereaptan A in a dry cleaning machine as follows:

1 η of the dry cleaning machine a solution is prepared that contains; n perchiorethylene 4% polymer aptane A. 0.08% diethylenetriamine and 0.2% cumene hydroperoxide contains. The garment is immersed in the solution and the machine is started. After impregnation, it is allowed to drain, then spun until it is 60% of its own weight in solution (2.4% polymer aptane). and then machine dried. Another one Deformation of the folds is not necessary.

The mercapto connection is then fixed by leaving it where it is. After 7 days the garment will washed according to the standard method for one hour, with a shrinkage in length of 1% and results in no shrinkage in width. The wrinkles show an average degree of fixation 89%. and the dryness softness index on the smooth areas is 4 to 5.

Examples 6-14

The textile material used here is a gray serge made of worsted ^{mixed wool, the weight of which is 270 g · m ~ 2} and the aqueous extract of which has a pH value of 7.8. The fabric is smoothed with 1.5% of its weight with monoethaiolamine sesquisulfite and then treated for 4 minutes in the rolled-up state with steam under atmospheric pressure. The fabric is cut into pieces and these samples are trapped by spraying them at the folds with 40 ", Ό 5% monoethanolamine sesquisulfite solution, folding them and treating them in the Hoffmann press as follows:

30 seconds of steam with pressing, 30 seconds of pressing without steam. Allow to cool under vacuum without pressing.

These fold patterns are now made with a solution of the Polymercaptan in perchlorethylene in the way padded. that the uptake of polymer aptane is 3% of the weight of the goods. Used as catalysts Diethylenetriamine or calcium naphthenate used, in amounts of 1 or 5%. based on the Amount of polymer aptane. It is fixed by storage at 20 Cur. 65% relative humidity. Then will the samples washed according to the standard method and then surface shrinkage. Dryness index and degree of fixation measured. Table II shows the results.

Table 11 l'olyrm-i- example cuptun D. 6th E.
i; 7th F. 8th
9 F. 10 G 11th G 12th H 13th I. 14th Untreated pattern

5% diethylenetriamine 1% diethylenetriamine 5% diethylenetriamine 1% calcium naphthenate 5 "" Calcium naphthenate 1 "/" Calcium naphthenate 5% calcium naphthenate 1% calcium naphthenate 5% calcium naphthenate

The table shows that excellent shrinkage resistance is obtained. Furthermore, the degree of memory is 75% or higher, mostly 85% ο the higher. The handle of the goods is very good, fuller and not harder than before. Likewise, the practical Drapiervermogen ⁱ SSS remains

Fixation?
UUUlT _; . Area
shrinkage I roi'kiiunus-
rtcichlicil-lnde » I old-
fi \ ii-iuni! -. grud
I ^u u I (Titgel (VuI 0.0 4 5 99 28 4.0 3 75 U 1.0 4th 96 O
2ö 0.0 4- 5 87 χ 1.0 4th 100 O
14th
14th
21 0.0
5.5
0.0 4th
3
4th 97
77
86 14th 1.5
14.0 4th
1 75
17th

The duration of the fixation varies, and it is found that the duration of the fixation can largely be adapted to the respective requirements by means of suitable combinations of catalysts and polymercaptans. The times given are not absolutely necessary for the fixation, they mean the time span between the ^ ^ of the Polymercaptan and the standard wash, and in

Table HI

Example polymer catalyst

captan

23
24
25th
llnbeh

K
K

L.
L.

A.
A.

M.
N
N
andcltes pattern

1% diethylenetriamine + 5% dilauryl peroxide 1 "/ o calcium naphthenate 4-5% Dilauryl peroxide 1% calcium naphthenate 1% calcium naphthenate + 5% dilauryl peroxide 1% calcium naphthenate 1% calcium naphthenal + 5% dilauryl peroxide 1% diethylenetriamine 1% diethylenetriamine 4

Dilauryl peroxide 1% calcium naphthenate 1% diethylenetriamine% calcium naphthenate

In some cases the fixation time may be shorter than indicated in the table.

Examples 15 to 25

The poly mercaptans are in the manner indicated in Examples 6 to 14 in the manner described there Textile material is applied, but in SeIn-P cases 1% Di-EhSÄmin is used as the catalyst system + 5% dilauryl peroxide or 1% CaI-c uinnaphthenate + 5% dilauryl peroxide used. In turn the treated specimens are tested in the manner indicated and the results are the , See Table III.

Fixation * - area duration shrinkage

(Days) I ⁰ / ")

14th 1.5 14th 0.5 14th 0.5 14th 1.5 14th 0.0 14th 3.0 7th 0.0 7th 0.5 21 0.0 21 1.0 21 0.5 14.5

Drying
softness index
1%) Wrinkles-
degree of resolution
(%) 4th 89 4-5 100 4-5
4-5 88
89 4-5
4-5 75
80 4- 5
4 5 94
88 3-4
4 5
5 76
90
81

These results again show that the materials treated according to the invention can be washed in the washing machine can be washed. The patterns also have a remarkably good grip, in particular this is the case with the samples treated with Polymcrcaptan A.

Examples 26 to 37

Examples 38 to 46

A flannel of about 170 g · m ~ ² , the aqueous extract of which has a pH value of 3.1, win ^{1 with} a solution of the polymercaptan in perchlorine .n, the. calculated on the polymercaptan, still contains Hi: υ monoethanolamine, treated on the padder in such a way that the weight absorption of polymercaptan is 8%. Then it is dried during 2 ¹ J ₂ minutes at 5o "c in the furnace under aeration so that it ι again has the original dimension, and are then left at room temperature for the indicated in Table IV time. Then, the flannel in a washing machine is in SO "C with a liquor containing 5 g of soap flakes and 2 anhydrous sodium carbonate per liter of water, washed with cold water, spun off and dried at 50" C. Table IV shows the results. Similar results are obtained with previously reduced or oxidized To reduce the flannel to a 50% weight gain, it is coated with an aqueous solution containing 10 g of sodium methabisulfite and 4 g of an adduct of nonylphenol and 9 mol of ethylene oxide and then dried for ½ minutes in the oven with aeration is increased to 140% weight with a liter of 20 ml of 30% (30 g of H ₂ O ₂ in 100 ml of solution) hydrogen peroxide, 1.2 ml of 85% ant acid and ι ü of the adduct just mentioned, ß _sune whose pH is adjusted to 3.7 with sodium carbonate, padded, the flannel stored for 4 hours in a polyethylene sleeve and then dried as indicated.

Table IV

example Polyraercaplan fixation
permanently Untreated (Days) Flat
shrinkage 1
9 <% l 26th B. 1
9 12.3
8.7 27 C. 1
5 12.2
5.5 28 P. 1
8th 11.7
10.5 29 Q 8th 11.3
7.0 30th R. 6th 12.5 31 S. 1
5 12.3 32 T 9 12.5
11.5 33 U 1 8.7 34 V 8th 7th 1
5 35 W. 18th 9.3
8.5 _t 5.5 I.
8th ft ^ς . 36 X 1
8th 5 37 Y 5.5
4.5 23.5

The poly mercaptans graze, dissolved in perchlorethylene, padded onto the textile material that the uptake is 4%. Knitted goods made from zephyr yarn are used as textile material. The Flotlenaufnahme is 200%, and the samples are then dried in the dryer at 60 ° C. Diethylenetriamine is used as the catalyst in amounts of 2%, based on polymercaptan.

The samples treated in this way are put in a washing machine after the polymercaptan is completely fixed subjected to the known washing test, in which the textile material first for 30 minutes in 25 liters and dyin for 60 minutes in 12.5 liters Wash liquor is treated. The washing machine is an internationally available machine for performing of wash samples. The cube-shaped container with a capacity of 50 liters is around one of the rooms diagonally rotatable. The speed is 60 per minute, the direction of rotation changes every 5 minutes with 5 seconds of standstill when changing. Table V shows the results.

Table V

! 5

'olymercaplan By S Fixation
length of time Flat
shrink (Days) <% | 38 D. -> 2 4th 39 E. 1") Jt 40 H 5 - 3 41 J 2 1 42 K 25th 5 43 A. 7th - 1 44 M. 10 45 N 2 1 46 C) 24 1 Untreated 72 game 47

From 3 parts of Polymercaptan A, 0.15 parts of monoethanolamine. 0.3 parts of an adduct of nonylphenol and 9 moles of ethylene oxide and 96.55 parts Water creates an emulsion. A piece of gray serge is used in that described in Example 4 Way with monoethanolamine (instead of sesquisulfitj smoothed and then impregnated on a padder with the emulsion to 100% weight gain, tension-free dried and left to fix the polymercaptan. The tissue becomes a Pants manufactured and. as described in Example 4, ι provided with creases. After 7 days the Pants washed according to the standard method. In the process, it shrinks by 0.7% and in length by 0.8%. After washing, the dry whiteness index is 5 and the degree of fixation of the

s len 85%.

In another embodiment, with a mixture of 320 g of Polymercaplan A, 144 g of water and 16 g of an adduct of 1 mole of stearylamine and

7OMoI ethylene oxide worked. Hog this preparation are mixed with 7.5 g Monoathanulam.n and 882.5 X water. Wool flannel is impregnated dam ο that the weight gain 110 / "Belra _{t t;} dried in the oven with ventilation and then left for 61 t. The flannel treated in this way is then washed in a washing machine at 50 ° C. with a liquor containing 5 g of soap flakes and 2 g of anhydrous sodium carbonate per liter. The fluff shrinkage is 6.5% with so bchandeKc flannel, 29.7% with untreated flannel under the same conditions in the laundry.

Example 48

A half-wool fabric made of 50% wool and 50% cotton is, as described in Example 4, with Monoethanolamine sesquisulfite fixed. The hold of it and a piece of the same, but not pretreated, half wool are put in the dry cleaning machine with a solution of polymercaptan A with the addition of 2.5% (based on polymercaptan) dialnylenetriamine impregnated as a catalyst so that the fabric retains 2.5% of its own weight polymercaptan. After the fixation for 7 days, garments are made from both pieces. Corresponding items of clothing are also made from nui pretreated with sesquisulfite and untreated at all Wool made.

The four garments according to the method Standai a washed, centrifuged and dried. They then result in the following drying softness indiees:

treatment

Dryness

weiclihuil-

Inde>, -

2 3

LJ η treated

Sesquisulfite only

Polymercaptan only 4

Scstiuisulfii and Polymercaptan 4 5

This means that achieved by the polymercaptan Improvement in the softness of drying, irrespective of whether a cold with sesquisulfite was found or not.

Examples 49 and 50

Jc a sweater made of lambswool and Shetland wool ν-earth first dry-cleaned and then with a l'ösiini: of 4425 Polymercaptan A and 88.5 g of diethyl triamine in 54.6 liters of perchlorethylene. impregnated After 3 minutes of impregnation, the Sweatei thrown off, so that the weight gain is still 60% ", turned cold for 3 minutes and then at 65 to 70 ° C for 10 minutes as by washing after 3 days in a household washing machine has been found, the sweaters have excellent felt resistance. The level after washing twice during each τ 10 minutes in a washing machine are as follows:

example

material

Lambswool
Shetland wool

PiMvmerca ptcn

3.08 2.85% 1 pool.

Re'axatious-

shrinkage

Examples 51 and 52

Double jersey made of wool is impregnated in the dry cleaning machine with a solution of 9.65 kg of Polymercaptan A and 195 g of diethylenetriamine in 159 liters of perchlorethylene. The piece of textile is circulated for 3 minutes, the liquid is allowed to run off into the storage container, the piece is spun at high speed for 7 seconds so that the uptake is 84.5%, and then dried ^{at 50 ° C. for 12 minutes.} The jersey has a soft feel, good stability in terms of recovery shrinkage and excellent felt resistance after washing after 3 days:

Va area,
Felt shrinkage % Gesanil-
shrinkage,
dry-dry 1 53 - 3.7 -0.7 -6.9 -3.2 B e i s ρ i e

(a) relaxation -
(b | laundry

example

15 minutes of wetting without movement

5 minutes in the washing machine 1 hour in the washing machine with 12.5 liters of washing liquor

% Polymercaptan

% % Surface.

Relaxation fizzying fun! shrink university!

150 g of Polymercaptan A and 22.5 g of an additive Rmsproduktes of nonylphenol and ethylene oxide in the molecular ratio 1: 9 are in the high speed stirrer mixed and processed into a permanent emulsion by gradually adding 327.5 g of water. This 30% emulsion is diluted to 3% then 5%. based on polymercaptan, diethylenetriamine added as a catalyst. A fabric made of Zephyr yarn is made on the padder with this emulsion impregnated and dried at 60 C. After fixation at room temperature for 14 days Wash tests have been carried out which demonstrate the excellent shrinkage resistance of the fabric treated in this way show.

% Poly-Cubex wash sample mercaptan% area shrinkage

30 minutes, 30 minutes. 25 liters 25 liters

Fleet fleet, then

W) minutes, 12.5 Liier

! - "Inllp

51
52
Untreated

3.2
2.8

0.0

5.4

5.6

13.2

1.5

1.6

16.3 53
Untreated

3.0
0.0

0.4 38.3

2.1 72.0

Example 54

A piece of worsted gray wool made with monoethanolamine sesquisulfite has been smoothed in the manner given in Example 4, is in the warp direction by spraying on a 5% monoethiinolaminosesquisulfite solution, with a liquor pick-up of 40% in the area of the fold, folds and treatment in the Hoffmann press (20 seconds Steam with pressing, 20 seconds pressing without ι ο steam, 10 seconds cooling under vacuum without Pressing) provided with a fold.

The fabric swatch is made with a solution in perchlorethylene from equal amounts of Polymercaptan A and impregnated a prepolymer polyurethane containing free aliphatic isocyanate groups in such a way that that it subsequently contains 0.75% polymercaptan and 0.75% polyurethane. Immediately after evaporation of the solvent, the sample was washed by the standard method and then the standard tests carried out, which has an area shrinkage of 0.5%, a drying softness index of 5 and a degree of wrinkle fixation of 100%.

Although the fixation of the agents used on the fiber takes place quickly, the bath remains stable and delivers the same results after 7 days.

Example 55

For comparison purposes, the following 4 preparations are made manufactured:

A. In accordance with the present invention

Polymercaptan A emulsion 4.5 g

Monoethanolamine 0.3 g

Wetting agent 0.2 g

Water 95.0 g

B. In accordance with the present invention, Polymercaptan A Emulsion 12.0 g

Monoethanolamine 0.8 g

Netzmiltel 0.2 g

Water 87.0 g

C. According to FR-PS 15 14 843 (Example I, solution B)

Thioglyccrine LS g

Dithioglyccrine 6.0 g

35

40

Wetting agent 0.2 g

Ammonia up to pH 9

Water on K) Og

D. Blind test

Wetting agent 0.2 g

Water 99.2 g

Ammonia to pH 9

Polymercaptan A is described in the manufacturing instructions. The emulsion of Polymercaptan A is obtained by

Polymercaptan A 66 g

Emulsifier (adduct of 1 mole of nonylphenol and 9 moles of ethylene oxide) .... 6.6 g

Water 27.4 g

mixed together with stirring.

The wetting agent used is an adduct of 1 mole of octylphenol and 8 moles Ethylene oxide.

A wool flannel (170 g / m ² ) is dried with preparations A, BC and D at a liquor pick-up of 100% foulardierl for 15 minutes at 85 ° C. and ironed under a damp cloth for 2½ minutes. After 3 days of storage, the samples are washed in a bath which contains 2 g of soap and 0.8 g of sodium carbonate per liter, the water ratio being 30: 1.

The samples are then rinsed in cold water and dried. After 16stündigcr storage at 20 ⁰ C and 65% relative humidity, the area shrinkage is measured or calculated from the change in linear dimensions:

45 treated

with preparation

A.
B.
C.
D.

% Planar shrinkage

5.4

5.4
19.2
18.3

This shows that the known preparation C about the same efficiency as that of the pure Nctzmitlellösung and about 3 ¹ / 211ml sizes area shrinkage permits than the eiiinduniisge · MAESSEN preparations A and B.

Claims (1)

Patent claims: ί. Process for modifying keratin-containing fiber materials, d a α u r c h ge mark-η e t that one contains these materials with at least two mercapto groups in the molecule Compound treated in the form of solutions in organic solvents or of aqueous emulsions, which ι ο