DE1494641C - Method of making thread - Google Patents

Description

The invention relates to a method for producing threads by spinning protein-containing threads Viscose in a usual bath.

These threads have excellent crimp and a woolly "feel", and they also have one high elasticity and kink resistance or flexibility.

It is already known that fibers that feel woolly or have a wooly "handle" through co-spinning a viscose with a protein can be obtained. The products rot and ι ο but decompose so easily that uniform and satisfactory fibers have been difficult to obtain. In addition, the kink resistance of the fibers produced in this way is very low and so is their tensile strength moderate. Although they come close to wool in some properties, they are therefore of little use and are hardly used.

There are fibers that are produced by spinning grain protein as a raw material and treating it Fibers can be obtained with formalin. The strength of these fibers is 1.0 to 1.5 g / den. Because they are feel like cashmere wool, it is recommended to mix it with other fibers to get the "feel" of the To improve products.

It is also from the essay by R. P u m e r e r, "Chemical textile fibers, films and foils" (1953), S. 387, known to spin a mixture of an unmodified protein and a viscose. However, the protein tends to be hydrolyzed by the alkali present in the viscose and also from the threads during the various manufacturing and processing stages to detach. In addition, such a protein is relatively easily dissolved and even in the threads The fibers are washed out during the dyeing process, washing or other treatments. In addition, it is difficult to keep the finished spinning solution unchanged to accommodate the various To carry out processing stages.

It is also known from French patent 830 101, a mixture of unmodified Spinning keratin and viscose. Because this material comes in the form of a simple mix with the unmodified protein is used, the various disadvantages mentioned above are also here given.

In contrast to this, a very special protein derivative is used in the present process, which is able to form a homogeneous and stable solution with viscose, the solution opposite Viscose is resistant to alkali, does not degrade and is resistant to water, so that the protein is not released from the threads or fibers obtained. Also, get the threads wool-like properties excellent due to the protein, excellent crimp properties and elasticity.

When a protein can be added to the viscose without the risk of decomposition and the formed Fiber mixtures too. Resistant products can be processed, so can synthetic fibers with excellent Create a "handle" and industrial use.

A method of co-spinning a synthetic resin emulsion of a protein graft polymer has been found Suggested with viscose to increase elasticity and water resistance of the viscose fibers to improve. The invention is the result of systematic studies of the relationship between molecular structure and colloidal character of protein derivatives and on the influence of such protein derivatives on synthetic fiber mixtures for the purpose of preventing putrefaction and decomposition of the protein as well as for Achievement of a uniform and stable mixture with this protein derivative.

The invention relates to a method for producing threads by spinning protein-containing threads Viscose in a conventional bath, which is characterized by the fact that a viscose is used as protein derivative containing a nitrile residue

1. hydroxyeyanoalkylated proteins,

2. cyanoalkylated proteins,

3. by treating these proteins 1 and 2 with aldehyde or a high molecular compound products obtained with an aldehyde radical or

4. Products obtained by graft polymerization of styrene, methyl methacrylate or methyl acrylate with these proteins 1 or 2 are obtained,

are added, the proportion of protein derivative 5 to 50%. based on the weight of the Mixture of fibers to be spun.

It was further found that threads with excellent crimp and a woolly "handle" and high elasticity and kink resistance by mixing an aqueous solution of such Protein derivative or an emulsion of such a protein graft copolymer with viscose and spinning of the Gernisches can be produced in the factory in the usual way.

Details of those to be used in accordance with the invention Protein derivatives and their joint spinning with viscose are explained below will.

1. Spinning of a mixture of viscose with a hydroxyeyanoalkylated protein which is substituted by an epoxy group by addition reaction Nitrile compound and a protein is produced

A nitrile compound substituted with an epoxy group can undergo addition reaction with the active hydrogen of an amino radical, a carboxyl or alcoholic hydroxyl radical of a protein enter in the presence of a basic catalyst, a protein derivative in the following manner, which contains a nitrile residue results in:

\\ - NH ₂ + CH ₂ ^: CH - (CH ₂ ) "- CN - ■ -» P _r - NH - -CH - CH ₂ - (CH ₂ ) "- CN ° OH

P _r denotes the protein's polypeptide, -NH ₂ the terminal amino radical of the protein, and / 1 is 0, 1 or 2.

So goes z. B. 2-Cyanomethyl-ethylene oxide with a protein an addition reaction to form a hydroxy-eyanopropylated protein:

P _r - NH ₂ + CH ₂ - CH - CH ₂ CN

If you give ζ. B. a protein 0.3 respond to a 5% strength sodium hydroxide solution ^s to 2.0 moles of 2-Cyanomethyläthylenoxyd per mole of amino acid residue in the protein added and the mixture 1 to 2 hours at 40 ° C, then an addition to smooth the alcoholic hydroxyl radical , the amino and carboxyl radical, and a hydroxy-cyanopropylated protein is obtained.

Compared to unchanged protein, this protein derivative has a higher resistance to putrefaction and resistance to alkali and can be mixed evenly. The one in the Fibers obtained by admixture usually have a woolly "handle" and are excellent Curl and kink resistance.

The nitrile compounds suitable for use contain epoxy radicals, such as. B. 2-cyanoethylene oxide, 2-Cyanomethyläthylenoxid etc., which is an addition reaction can enter into the active hydrogen of a protein.

Since these nitrile compounds have an active epoxy group, the addition reaction takes place with them the protein quantitatively.

Basic compounds are suitable as catalysts

IO

20 P _r -NH-CH-CH ₂ -CH ₂ CN

OH

genes such as sodium hydroxide, potassium hydroxide, primary, secondary and tertiary amines, and salts of amines. The reaction can be carried out under suitable reaction conditions in a temperature range from 10 to 90.degree and carried out with a reaction time of 10 minutes to 5 hours.

The proportion of protein derivative that can be added to the viscose is 5 to 50%, preferably at 10 to 30%, based on the weight of the fibers to be spun from the mixture.

2. Spinning a blend of viscose with one

cyanoalkylated protein produced by addition reaction

a nitrile-substituted, unsaturated Ethylehverbin-

is obtained with a protein

Unsaturated ethylene compounds with a nitrile radical that is strongly negative for a protein are substituted, can be activated in the presence of an alkaline catalyst and then leave an additive reaction of the Michael reaction type with the active hydrogen on the protein, whereby a cyanoalkylated protein is formed in the following way:

P _r -NH ₂ + C

A; and A ₂ are H or a CH ₃ radical, A ₃ is H, a CN radical or a CH ₃ radical. When using tetracyanoethylene or vinylidenecyanide, a tetracyanoethylated protein or an ovu-dicyanoethylated protein is obtained in the following way:

. . 'CN
P _r -NH ₂ + C =

CN

CN

CN

basic catalyst '

V ^ " r, in rl v_ ^

CN
/ CN

P _r - NH ₂ + CH ₂ = C

basic catalyst

CN

CH, C

CN
CH

CN
/ CN

^S CN

If z. B. 'are added ge ⁿ aqueous sodium hydroxide solution dissolved protein 0.3 to 3.0 moles per mole Tetracyanoäthylen amino acid residue in the protein and is 2 to 3 hours causes an addition reaction at 50 "C,' a in a 5% so formed a tetracyanoethylated protein.

The protein substituted with nitrile radicals produced in this way is resistant to putrefaction and decomposition and can be combined with viscose to form a stable mixture. When spinning Mixing in the usual way produces fibers with a woolly "feel" and excellent crimp and kink resistance obtained.

The unsaturated ethylene compounds substituted with nitrile radicals, which are used in the present invention, are reagents in which the nitrile group has a + Ε effect on the - CC- bond of the active unsaturated radical, ie the ethylene, vinylidene or vinyl radical , goes out.

Among these unsaturated ethylene compounds are nitrile compounds with ethylene radicals and Vinylidene radicals, such as. B. tetracyanoethylene, tricyanoethylene, vinylidenecyanide, methacrylonitrile and u-chloroacrylonitrile and nitrile compounds with one Vinyl radical such as acrylonitrile. They can be used individually or as a mixture of two or more these substances are used.

Suitable catalysts are strongly basic compounds, such as basic inorganic salts, e.g. B. Sodium hydroxide, potassium hydroxide, potassium cyanide and sodium cyanide, also quaternary ammonium hydroxides, like trimethylbenzylammoniumhy-

hydroxide, dimethyl - phenyl - benzyl - ammonium hydroxide etc.

Since the nitrile compounds listed above have active unsaturated radicals, they react in the presence a basic catalyst easily with a protein, but the reaction becomes preferable in a temperature range from 20 to 90 ° C and with a reaction time of 20 minutes to 5 hours accomplished.

The proportion of protein derivative that can be added to the viscose is 5 to 50%> preferential

NC- (CH ₂ J ₁₁ -HN-P _{1. -NH 2} + RCHO wise at 10 to 30%> based on the weight of the fibers to be spun from the mixture.

3. Spinning of the mixture of viscose with a protein derivative obtained by treating the items 1 and 2 named proteins with aldehyde or a high molecular weight compound with aldehyde residue is obtained

When an aldehyde compound is used with the above-mentioned nitrile substituted derivative, e.g. B. a cyanoalkylated protein, a derivative of this protein is obtained in the following way:

-> NC - (CH ₂ ) _n —HN-P _r —NH-C —R

OH

R is hydrogen, an alkylene radical with 1 to 4 carbon atoms, - CH = CH ₂ or a high molecular chain.

If z. B. used a hydroxy-cyanopropylated protein as a nitrile-substituted protein derivative and a Vinyl alcohol-acrolein copolymer of a high molecular weight aldehyde reacted with this protein derivative the following protein derivative is obtained:

H ₂ N - P _r - NH - CH - CH ₂ CH ₂ CN + - CH ₂ - CH - CH ₂ - CH - CH ₂ - CH

OH L OH CHO

TCH ₂ - CH - CH ₂ - CH - CH ₂ - CH - I OH HO —CH OH "

OH

NH - P _r - NH - CH - CH ₂ - CH ₂ - CN OH

As a specific example, the following is cited: When 33 mol percent allylidene diacetate and 67 mol percent vinyl acetate are copolymerized with one another using azo-bisisobutyronitrile as a catalyst and 15 percent by weight of a vinyl alcohol-acrolein copolymer obtained by alkali saponification of the product of the above copolymerization , hydroxy-cyanopropylierten to an alkaline solution of a protein are added and the mixture was reacted at 30 to 50 ⁰ C for 2 to 3 hours, so the desired protein derivative.

In this derivative, the aldehyde residue and the amino residue of the protein are linked to one another, and the aldehyde radical of the acrolein molecule is free. Therefore, when the named derivative is heated, a Crosslinking between a polypeptide chain and an active hydrogen atom of the cellulose, and that The product becomes insoluble in alkali. The fibers spun from a mixture of this protein derivative with viscose show a particularly good resistance to alkali. The protein derivative is easy to mix with viscose. A mixture of the protein derivative with viscose can be spun excellently, and the Fibers made from this mixture have a woolly "handle" and are excellent Curl and great strength.

The nitrile-substituted protein derivatives that are used in the reaction with the aldehyde are not limited to those listed above, but can be any in the sections 1 and 2 can be used.

As aldehyde compounds that can be used in the above-mentioned reaction, low molecular weight aldehydes such as adipaldehyde, glyoxal, Butyraldehyde, acetaldehyde, formaldehyde, acrolein, methacrolein etc., and high molecular weight aldehyde compounds, such as polyacrolein, polymethacron, dialdehyde starch, dialdehyde compounds, which by opens the 1,2-glycol bond of polyvinyl alcohols are obtained, as well as polyvinyl alcohols with aldehyde residues, which are obtained by saponification of the Copolymers of allylidene diacetate and vinyl acetate are obtained. Also a mixture of two or several of these aldehydes can be used. If desired, the connections can also be saved as Use addition products with sodium sulfite in the reaction.

The aldehyde compounds listed above react quite quickly with the crude protein to form of a gel, and the reaction is difficult to control. The invention, nitrile-substituted Protein derivatives react more slowly and because of the strong effect of the nitrile group more uniform with these aldehydes so that a stable and uniform solution will result.

As catalysts in the above reaction

between an aldehyde and the protein derivative alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium phosphate etc., to be used. The reaction can take place in a temperature range from K) to 70.degree. C. and with a reaction time of 30 minutes to 3 hours. the However, reaction is not limited to these conditions.

The proportion of aldchydbcheltencm protein derivative that can be added to the viscose is included about 5 to 50% (preferably K) to 30%). based on the weight of your mixture to be spun Fibers. The mixture can be spun or shaped into fibers in the usual way.

Hs is not necessary, the fibers obtained a Submit post-treatment with formalin. However, if the fibers are heat treated, it leaves the content of protein equivalent (in the fibers), which is resistant to alkali, increases even further.

4. Spinning of a mixture of viscose with a protein derivative containing a nitrile radical, which was obtained by graft polymerization of styrene, methyl acrylate or methyl methacrylate with proteins mentioned under 1 or 2

If an unsaturated monomeric ethylene compound, such as a monomeric vinyl or vinylidene compound, in the presence of a polymerization catalyst with a nitrile-substituted protein is derivative graft copolymerized, a graft polymer with a obtained polymeric vinyl or vinylidene branching.

Vinyl or vinylidene compounds are styrene,

Methyl methacrylate or methyl acrylate. If both

'5 for example styrene with one in an aqueous alkali solution dissolved (», (- / - dicyanoethylated protein under If hydrogen peroxide is used as a catalyst, the following graft polymer is used obtained as a white speckled stable emulsion.

20th

CH = CH,

/ CN

.-NHCH ₂ HC

CHCH ₂ NH-P _r -NH

NC ^/ - [ch ₂ -ch] "

We have found that the solution of the monomer Vinyl or vinylideii protein graft copolymers is so resistant to rot that it is combined with viscose to form a permanent mixture can be. If such a Pfropfpolymerisal emulsion mit.Viskose mixed and in is spun in the usual way, the result is fiber mixtures with a woolly "handle" and higher Maintain elasticity.

The nitrile-substituted protein derivatives used according to the invention in the copolymerization are not particularly limited, and those in Sections 1 and 2 above can be used Use the connections listed.

Even when about 20% (parts by weight) or more (based on the weight of the cellulose component) of graft copolymer is added to a viscose, no noticeable reduction in the strength of the (spun) fibers produced from such a mixture can be observed. If the emulsion of the graft copolymer is spun mixed with viscose and the strength of the fibers formed is markedly reduced, this disadvantage can be avoided by adding a small amount of a surface-active agent to the spinning solution. Also, by addition of a small amount of a water-soluble polymeric solvent, the reduction of strength can be limited to a minimum S ⁵ are.

When a monomeric vinyl compound is graft copolymerized with a protein alone, the protein becomes significantly more resistant to putrefaction. But if z. B. the protein was previously dicyanoethylated, this effect is even more noticeable. The cyanoethylation or the cyanoethylation can be carried out by reacting acrylonilril or vinylidenecyanide with an alkaline solution of the protein. In such ^ ⁵ implementation unused acrylonitrile or vinylidene remain. Therefore, the method is in which the remaining, non-set (substituted with a nitrile group) monomer is graft-polymerized with the dicyanoethylated protein with the addition of a polymerization catalyst. Industrial practice is an advantage. '■

The graft polymerization can also be carried out with the addition of monomers such as. B. styrene, methyl or Methyl methacrylate, the monomers substituted with nitrile (e.g. acrylonitrile, tetracyanoethylene, vinylidenecyanide etc.) «-» are polymerizable. Excellent dyeability for basic dyes are obtained when methyl acrylate is copolymerized. ,.

The results obtained regenerated Cellulose fiber !! which is a graft polymer of a nitrile substitute Proteins with a synthetic resin are resistant to water, but swell somewhat with alkalis. However, treatment with formalin makes them completely water and alkali-resident.

Aqueous polymerization is suitable for producing the nitrile-substituted protcin derivative-synthetic resin copolymer which is to be mixed with a viscose. It is therefore advantageous if the polymerization is carried out in an alkaline protein solution, the emulsion produced is mixed with a viscose and then spun. In I ⁷ alic the alkaline solution of the polymerization catalyst is limited to particular substances, but there is an advantage that degree of polymerization and yield of the graft copolymer is high. In the event that the rate of polymerization and the degree of polymerization are low, these disadvantages can be overcome by using a redox polymerization system such as a hydrogen peroxide-amine system or a hydrogen peroxide-sodium sulfate system, depending on the monomer used;

A water-soluble one is suitable as Ka (al \ salor Peroxide, such as ammonium persulphate, - potassium persulphate. or hydrogen peroxide, in an amount from 5 to 0.2 ", based on" the weight of the monomer. the The polymerization temperature in this case is

Range from 20 to 85 C. As a reducing agent in the Redox catalyst systems are 5 to 0.1% sodium sulfite, acidic sodium sulphate or sodium thiosulphate. The suitable polymerization temperature is in this case at 30 to 60 "C.

As already stated above, all protein derivatives used according to the invention are so-called nitrile-substituted protein derivatives, in which a nitrile compound has various functional parts Can carry groups through a chemical reaction in place of the active hydrogen one Polypeptide has been stirred into the protein.

In general, such protein derivatives can be characterized in the following way:

1. Through the influx of the nitrile group bound to the protein molecule, the protein derivative becomes Fill-resistant and stable. Regardless of the substituent, the nitrile radical is attached to the polypeptide structure bound. The higher the content of nitrile groups, the stronger the effect.

2. The colloidal properties of the aqueous solution of the protein derivative are different from those of the Alisgang protein. Even if the solution is mixed with viscose in any ratio the transparency of the solution does not change and the spinnability is excellent. A spinning solution can therefore be produced without gelatinization or separation entry.

3. When preparing the spinning solution, 10 up to 30 parts of protein derivative mixed with viscose in such a way that 90 to 70 parts of cellulose component can be used in viscose. The mixture is from nozzles into a common Precipitation bath extruded (to form crimped fibers).

4. The fiber mixtures produced in this way have a high kink resistance, a woolly "handle", have many crimps and are of high elasticity. These ripples in particular are very persistent. In the following the features are given in an example.

Degree of curl (%),
original sample

Degree of curl (%) of the with
Soda smoothed sample ...

Degree of curl (%) of the
then with steam
treated sample

Curl recovery (%)

According to the invention
Fibers

28.0
12.5

21.0
85

Ordinary staple fibers

21.2
9.3

14.8
69

Compared to ordinary staple fibers, the fibers according to the invention have a significantly higher level Initial crimp and also have higher crimp recoverability when the fibers are first stretched by mechanical action and then treated with steam.

This is a property of great importance because the fibers are usually spun, Weaving and processing subjected to numerous mechanical influences and heat treatments, before they are finished to end products. If the loss of frizz with these treatments is large, the effect is lost. In view of these properties, it can be said that the invention Fiber blends retain their original high crimp ability and in it the usual Staple fibers are superior.

The 10% stretch elasticity of fiber aggregates, which is created by spinning viscose together with a derivative made by

ίο further implementation of a high molecular weight aldehyde with a nitrile-substituted proline derivative or with a through. Graft copolymerization a ClL-C substituted monomers with a protein obtained graft polymer are produced, shows .ein value that with acrylic acid synthetic fibers can be compared. The fiber mixtures obtained according to the invention therefore differ clear in their properties of ordinary staple fibers.

Examples of proteins that can be used according to the invention are cow's milk casein, grain protein casein, Soybean protein, peanut casein, etc. are listed.

B e i s ρ i e 1 1

A mixture of 110 g (absolute dry weight 100 g) casein, 400 g water and 23 g sodium hydroxide were stirred for 5 to 10 minutes. Then 28 g 2-Cyanomethyl-ethylene oxide was added to the solution, and the addition reaction was carried out with stirring at 45 "C in 3 hours. The cyanopropylated protein-containing solution prepared in this way was on Cooled to room temperature and with 169 g of 20% aqueous .Natriumhydroxydlösung and 3800 g of viscose mixed. The mixture was decolorized and spoiled. The spinning bath contained 7.5% sulfuric acid, 28.0% sodium sulfate and 1.2% zinc sulfate. The other spinning conditions did not differ of those used in the conventional spinning process for making crimped viscose yarns.

The fibers were then treated with formalin, desulphurized and subjected to the usual post-treatment. During the formalin treatment, the fibers were treated with a solution of 5% at 60 "C for 2 hours. Formalin and 15% sodium sulfate treated.

The fibers obtained showed the following properties:

Denier 2.32

Dry strength 2.44 g / den

Wet strength 1.57 g / den

Dry elongation 16 () "/"

Wet elongation 17.7%

Crimp degree 14, t%

Number of crimps 16.1 / 25 mm

Buckling strength 536 times

The fibers had excellent curling properties, a woolly "handle" and a high kink resistance.

Be i s ρ i e 1 2

KM) g of casein were dissolved in 9 (X) in 1 of a 0.5% sodium hydroxide solution. Then 40 g Tetracyanoethylene was added to the solution with stirring. After the reaction lasted for 90 minutes 50 "C had expired, tetracyanoethylated casein was obtained in the form of a stable solution. The conversion was 25 "/ ,,. 2 (X) g of this solution were mixed with 2 kg of viscose, and the mixture was

spun into fibers in the manner described in Example 1. The physical properties of the fibers produced are given in the following table. The fibers showed excellent Ability to crumple, a woolly "handle" and a high degree of resistance to buckling.

Physical Properties

denier

Dry strength (g / den) ...

Wet strength (g / den)

Dry elongation ("/")

Wet stretch

Crimp degree (%)

number of

Crimps / 25 mm

Kink resistance

rehearse

Inlaid fibers

2.86 2.65 1.86 14.8 17.3 24.8

18.5 894 times

ordinary ίο staple fibers

2.85 2.81 1.75

21.0

23.7

19.8

11.2 1265 times

Example 3

100 g of casein were added to 750 ml of a 1% strength aqueous sodium hydroxide solution, and the mixture was stirred for 30 minutes. Then 25 g of acrylonitrile were added to this casein solution, and the condensation reaction took place within 2 hours at 60 ° C. It was thus cyanoethylated Obtained casein in the form of a solution. After cooling, this solution was mixed with viscose, so that the ratio of cellulose to casein was 87:13. The mixture was then like described in Example 1, spun into fibers. The physical properties of the fibers are in in the following table:

Physical Properties

Dry strength (g / den)

Wet strength (g / den)

Dry elongation (%) · · ·

Wet elongation (%)

Buckling resistance, times

Degree of curl (%) · · ·
number of

Crimps / 25 mm.
Crimp elasticity

Degree (%)

rehearse ordinary
Staple fibers invention
appropriate
Fibers 2.82 2.66 1.78 1.82 21.5 15.9 23.7 17.3 849 ' 1205 19.8 ' 24.4 11.0 19.8 49.0 60.8

35

and the initial temperature rose to about 80C. After the majority of the vinylidenecyanide had been polymerized, the temperature fell again to 75 ° C. After the reaction was continued at this temperature for 3 hours, a stable emulsion with slightly white spots had formed. The proportion of polymerized vinylidenecyanide was about 83%. K) Og of this emulsion were mixed with 2 kg of a viscose, and the mixture was spun into fibers which, after post-treatment with the usual methods, were used for the production of crimped staple fibers. The fibers recovered had excellent crimp and "hand". The strength was 2.78 g / den and the elongation was 18 ¹ V ₁₁ . The recovery in elasticity during an elongation was 56%. For comparison, it should be noted that ordinary staple fibers have a strength of 2.83 g, an elongation of 11% and an elasticity recovery of 48% with a 10 % elongation.

Example 5

K) Og casein were dispersed in 671 g of water, and then this dispersion was added dropwise with stirring with 72 g of a 10 "strength aqueous sodium hydroxide solution offset. The mixture was further stirred for about 30 minutes. Then were 25.0 g of acrylonitrile added to the solution; the addition reaction took place with stirring for 3 hours Solution at 55 ° C. Then 2 moles of acrolein (1), 2 moles of formaldehyde (2) and 1 mole of dialdehyde starch were added (3) added to the protein, and the addition took place within 2 hours at 50 C. The reaction product was mixed with cellulose in such a way that that the ratio of cellulose to casein was 9: 1, and then spun into fibers in the usual manner. The following results were obtained.

As can be seen from the table above, the kink resistance and curling ability have been improved, and the fibers had a woolly "handle".

Example 4

100 g of casein were in 9 (K) ml of 0.5% sodium hydroxide solution solved. Then 60 g of vinylidenecyanide were mixed with this solution. While stirring the mixture was kept at a temperature of 75.degree. When adding 3 ml of 30% hydrogen peroxide sets the polymerization of the vinylidenecyanide

1 2 'raw no 3
t unconcerned
acts "* ° Physical properties 2.90 2 Added amount of Alde 2.51 hyd compound (Mol 15.4 1 Nothing percent) 15.5 2 2.90 2.90 denier 2.86 2.54 2.48 Dry strength (g / den) 22.0 2.58 13.9 17.8 Dry elongation (%) .. 1307 14.6 18.8 13.0 ⁵⁰ degree of crimp (%) ■ · 16.8 Number of ruffles 12.1 22.6 14.2 lungs / 25 mm 93.4 22.8 648 535 Buckling resistance, sometimes ... 834 55 Solubility (%) in 11.0 18.5 6% alkali 12.0 96.8 83.0 Protein Retention (%) · · · 96.0

As can be seen from the table above, strength, curlability, alkali resistance and Noticeably improved retention.

B e i s ρ i e 1 6

167 g (absolute dry weight 150 g) were treated with Casein 1269 g of water and 30.9 g sodium hydroxide solution 2T7 _0, and the mixture was stirred for 1 hour. Then 33.5 g of 2-cyanoethylene oxide were added and the reaction took place

within 2 hours at 45 C with formation of / -hydroxy-eyanoethylated casein. Then a 10% solution was prepared of a copolymer separated by dissolution in a 1 ^{0 /} ₍₎ igcn borax solution which had been obtained from · 33 mole percent of acrolein and 67 MoI prozenl vinyl alcohol. Of this solution just described, 30 g were added directly to the cascine derivative, so that the mixing ratio was 50: 1. The mixture was reacted by stirring for 2 hours at 20 ° C. The solution obtained was made up of 16,875 kg of viscose with a normal cellulose concentration of 8 "" mixed. The ratio of cellulose to casein was 9: 1. During spinning, a precipitation bath of the same composition was used as is used in the spinning of the ordinary casein-viscose mixture. Compared with the casein mixed with hydroxycyanoethylated fibers were not affected in the produced fibers "handle". yarn quality and tensile strength, the protein loss after spinning and washing test was low, and it showed an increasing trend of 5 ° _n owned Dehnungsclastizität and Hrmüdungsbeständigkeit. As an example of these properties is the following comparison is given: The comparison fibers were under The properties of the fibers obtained, as well as those made from a mixture of -hydroxycyanoethylated casein and viscose, are shown in the following table. The properties of common staple fibers are also given.

Protein retention coeifi / .ienl:

The nitrogen content was determined after each wash, assuming that the The nitrogen content of the starting fiber is 100.

B e i s ρ i e 1 7

There were different monomers each in an aqueous, alkaline solution of cyanoethylated Casein prepared in the manner described in Example 2: polymerized. Polymerization conversion and composition of the emulsions obtained at 75 ° C. within 4 hours are listed in the same Table A.

Table A.

\ Hrfin- Ver Habit Physical Properties manic
according to equal
fiber liche
stack l-'ascrn fibers denier 5.10 5.06 5.08 Dry strength (g den) 2.87 2.81 2.80 Dry elongation ( ^(> / o) .. 18.9 17.8., 17.9 Degree of curl (° ") .. 24.6 24.1 13.4 Number of ruffles lungs 25 mm 22.4 20.5 14.2 5 ^l '/ () iger expansion degree of elasticity (° ") .. 52.1 46.7 42.5 KnicMFlexibility-) strength, times 869 672 520 Protein retention ■ efficient Before washing ... 100 100 - After 4 hours . To wash 86.3 69; 8 After hours To wash .70.4 60.1 -.

Remarks:

Washing conditions: Laünder-o-mcler method
Bath composition: ■:: · "

0.5 percent by weight of Marseilles soap and
'■ 0.2 percent by weight Na ₂ CO.,

Temperature: 70 1 2 C

Cyanoethylated casein solution:

Concentration ("/ <>)

Amount (g)

Ml water).

3% igcs H ₂ O ₂ (ml) .....

Monomer (g).

Polymerization conversion (%)

Composition of
Emulsion after the
Polymerization ( ⁽ '/ ₀ )
Cyanoethylated

Casein

Polymer

l'cisuch ^ Jr. G 1 (i 2 11.90 11.88 168 168 14th 14th 6th 6th Sl. 20th MMa 20 99.5 97.8 9.68 9.65 9.68 9.45

(> 3

12.66 168

14 6 MA 20

79.9

10.17 9.60

The physical properties of the individual emulsions by spinning together with Fibers obtained from viscose are listed in Table B. Both "grip" and curl ability were Well. The fibers had good elasticity.

Table B.

Physical Properties

Fineness (denier)

Firmness (g / den)

Strain ("/")

Elasticity recovery
in percent for one
10 ⁽¹ / _o igcn elongation ...

Attempt no.

6 1
3.94

2.58 15.6

51.0

6 2 6-3 2.93 3.13 2.66 2.78 18.5 16.3 55.6 59.0

ordinary staple fibers

2.96 2.68 20.2

41.6

Note: In the table, the monomers styrene with St, methyl methacrylal with MMA and Methyl acrylate abbreviated as MA.

Claims (4)

Claim: Method for producing threads by spinning protein-rich viscose in a normal bath. as a result of the fact that a viscose is used which, as a protein derivative containing a nitrile radical, 15 16 1. hydroxycyanoalkylated proteins, from styrene, methyl methacrylate or methyl 2. cyanoalkylated proteins, acrylate with these proteins 1 or 2 3. by treating these proteins 1 and 2 are retained, with aldehyde or a high molecular weight compound. ,,. ,. ., _. ,. _t Binding with aldehyde residue products obtained ⁵ f set s _{md> where} the proportion of protein inenvate _{0 (} j _er ^J 5 to 50%, based on the weight of the from the 4. Products that are fibers to be spun by graft polymerization mixture.