DE1118151B - Method for sizing textile yarns - Google Patents

Description

The invention relates to a method for sizing textile yarns. These can be made from threads or from Fibers consist of natural, semi-synthetic or synthetic types and be twisted or not twisted.

In order to give textile yarns resistance to mechanical processing, the yarns are made in front of the mechanical processing finished. Aqueous solutions of sizes are mostly used for this. Well-known water-soluble sizes are:

1.Sizing based on starch or protein,

2. derivatives of cellulose or starch,

3. Sizing based on polyvinyl alcohol,
Polyacrylic acid, polyacrylates and styrene maleic acid derivatives.

For hydrophilic textiles such as cotton, wool or viscose silk, sizes from groups 1 and 2 applied. Strongly hydrophobic yarns are sized with products of the third group. Cellulose acetate yarns can be sized with both protein products and synthetic agents.

It has been found that good results are obtained when textile yarns are mixed with an aqueous solution water-soluble ethers, esters or acetals of the amylose size and the treated yarn dries. Of the Surprisingly, the effect achieved when sizing with these amylose derivatives is not exceeded only in many points that of the products of the first and second group, but they also result also at least as good results as the products of the third group.

Sizing with amylose ethers is particularly important and the invention is therefore described in US Pat essential described with reference to these ethers.

The amylose ethers are the water-soluble alkyl, oxyalkyl and mixed alkyl and oxyalkyl ethers with 1 to 4 carbon atoms in the alkyl or oxyalkyl group. The alkyl or oxyalkyl group must not be too large, because otherwise the aqueous solutions of the amylose ethers in the for Sizing usual concentration, e.g. B. 5 to 10%> in the heat tend to have a on the surface To form skin. You have to have at least 1 alkyl or oxyalkyl group per 7 anhydroglucose units of the Introduce the amylose molecule to form sizing solutions that are stable in both cold and warm water to obtain.

The above applies both to amylose ethers for sizing hydrophobic yarns and to amylose ethers for sizing hydrophilic yarns. If you want oxyalkyl ethers for sizing hydrophobic yarns apply, it is a product of higher substitution process for sizing textile yarns

Applicant:

W. A. Scholten's Chemische Fabrieken N.V., Groningen (Netherlands)

Representative:"

Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald,

Dipl.-Chem. Dr. phil. H. Siebeneicher

and Dr.-Ing. Th. Meyer, patent attorneys,

Kölnl, Deichmannhaus

Claimed priority:

France of March 24th (No. 761 390)

and June 23, 1958 (No. 768 604)

Dr. Jan Lolkema, Geert Moes, Hoogezand,

and Willem Freerk Vogel, Groningen (Netherlands), have been named as inventors

grades, ζ. B. with an oxyalkyl group per 2.5 anhydroglucose units, apply. Alkyl or oxyalkyl ethers which also contain an aromatic group, for example ethylbenzyl ether or oxyethylbenzyl ether, are also suitable for this purpose. ^;

Amylose ethers with hydrophilic groups in the substituent are named for sizing hydrophilic yarn types into consideration. Examples of such ethers are the amylose ether carboxylic acids and amylose ether sulfonic acids as such or in the form of their salts, e.g. B. the alkali salts. Also are for this purpose Aminoalkyl ethers and aminoalkyl ethers substituted in the amino group are suitable.

The amylose raw material is preferably the linear fraction that occurs when starch is broken down into its components is obtained. This faction can do both can be used in the pure as well as in the impure state. For the production of amylose ethers it is advantageous to process the fraction without intermediate drying.

Instead of amylose preparations obtained by breaking down starch, native types of starch can also be used use that already have a high amylose content, such as the starch of certain types of corn.

109 747/532

Those used according to the invention. Amylose- The sizing solutions used can besides

ethers are produced by adding small amounts of amylose ethers to the amylose ethers Way contain the etherifying agent in the presence of the sizes usual auxiliaries, eg. B. Soft-required catalysts, in particular alkaline machiners, wetting agents or the like. The amylose ethers can Substances in an aqueous medium on the amylose-5 also used together with other sizes lets work; if necessary, the etherification can become.

can also be carried out in an organic solvent, which are yarns sized according to the invention

z. B. amylose becomes resistant to mechanical influences when heated under atmospheric conditions; they are covered with thermal or increased pressure, optionally in a strong, elastic, smooth film. The presence of peptizing substances in water, especially in the weaving mill, are dissolved with these yarns, with the etherifying agent and required good results are obtained. Another advantage of the addition of alkaline substances and the amylose ether reaction is that static charging of the yarns which are sized at normal or elevated temperatures is not listed or is practically not listed. For use according to the invention occurs. Furthermore, after the interweaving of the amylose ethers, the 15 yarns can easily be washed out of the reaction mixture,
to be isolated. In many cases, however, it is sufficient to use starch ethers and esters

Dilution of the entire reaction mixture with impregnation of fibers, especially as To use water on a concentration, sizing and finishing agent suitable for sizing, the tration. Starch ethers and esters either in finished form or

In practice, it may be important to use the 20 in the form of a source starch, a veräthe amylose ether in the form of dry products or esterifying agents and optionally put into circulation. These can exist through a catalyst when dissolving in water Isolate the amylose ether from the reaction mixture, starch ether or starch ester-forming mixture is used Cleaning and subsequent drying can be obtained. These strength ethers or stars will. Such isolation and purification is in 25 opposite but with the amylose ethers and not required in most cases. Dry product esters according to the invention give considerably better results very good properties are obtained by achieving nits. In particular, leave those with these If you put the entire reaction mass on heated rollers with amylose derivatives, sizing was achieved significantly dries and the film formed into flakes is washed out more easily and more completely, which by no means ground to the desired size. One must, however, expect it to be 30, since the amylose itself is precisely the in in this case ensure that the degree of substitution water sparingly soluble component of the native the amylose ether is not so high that the mass represents starch.

on the heated roller becomes plastic, so that it is more water-soluble

no longer described in the form of a thin film of the amylose ether. Instead of this ether can Can be removed from the roller. Difficulties of this kind include water-soluble amylose esters or acetals occur z. B. usually apply to alkyl and oxyalkyl ethers, in particular in the case of hydrophobic ethers only when the amylose ether more than one yarn, z. B. water-soluble amylose esters of Alkyl and / or oxyalkyl groups per anhydrous saturated or unsaturated fatty acids with contains glucose unit. at most 4 carbon atoms, such as acetic acid, pro

Suitable etherifying agents for the production of 4 ° pionic acid, butyric acid, acrylic acid and methacrylic amylose alkyl ethers include alkyl acid. Halides, dialkyl sulfates, alkyl tosylates and diesters with hydrophilic substituents, e.g. B. amylose azomethane. Estercarboxylic acids and amylose ester sulfonic acids can be used to produce the oxyalkyl ethers.
one alkylene oxides or alkylene chlorohydrins come from the amylose acetals in particular

turn around. _ 45 products made with formaldehyde are considered.

For the preparation of mixed ethers one can also use amylose derivatives, which both

Amylose contained at the same time or in sequence with ether groups as well as ester groups, as well the etherifying agents required for this are amylose derivatives, which in addition to ether and ester groups Act. Contain acetal groups. The latter is obtained by

The treatment of the yarns with aqueous solutions 50 that one amylose ether or ester with formaldehyde of amylose ethers according to the invention takes place after lets react. An amylose benzyldene is used as an example common methods for sizing yarns, called ether, which after benzylation with Formz. B. Immersion of yarn strands in the size that is treated with aldehyde.

Passing the yarns through a sizing solution In the examples below, the

or spraying a sizing solution or sizing yarn on some for the assessment of the bring by means of a roller. The yarns treated in this way have a characteristic sizing effect tested on heated drums or in heated shafts. Have the numbers mentioned Drying rooms dried. the following meaning:

For good penetration of the solution into the yarn The size number is the measure for the cohesion of the size bath, preferably on a slope of between 60% of the filaments. The first sizing number was kept at a temperature of 30 and 90 ° C. This refers to the beginning of the dissolution the element concentration of the sizing solution can vary; thread, the second number on the complete solution of the good results are obtained when the thread is 2 to connect these threads. A higher number 10 ° / ₀ receives the dry sizing. The pH value therefore means good sizing. All values are the sizing solution can also be within another 65 mean values of at least five tests.
Limits vary; for sizing cellulose- The values for breaking strength and elongation

acetate yarns, the pH of the solution should not be higher according to a normal dynamometric beal Be 8.0. Mood mood.

The smoothness is expressed in the number of seconds a thread of a certain length spends the first time. takes the tenth pass through a smoothness meter. Low values mean high values Smoothness degree.

The friction resistance is a measure of the resistance of the sized yarn to friction. A high value means high frictional resistance.

example 1

A 75 denier chain of acetate silk is continuously passed through an 8% aqueous chain at 60.degree

IO solution of an amylose ethyl ether (degree of substitution 0.40) run, whereupon the yarn is pressed off. The same experiment is carried out with a solution of an ethyl ether of tapioca flour with a corresponding degree of substitution. For comparison, the same yarn is also sized with a synthetic copolymer based on styrene maleic anhydride, which is particularly recommended for sizing acetate silk. It is dried on drums at 80 to 90 ° C.

The following results are obtained:

plain

Degree of substitution

Concentration sizing

strain

Smoothness

first time

tenth time

Seconds

Amylose ethyl ether

Starch ethyl ether

Styrene maleic anhydride copolymer

0.40 0.40 1.8 to 8.8
1 to 3.2

1.2 to 6.4

14.4
14.9

9.3

2.2 2.7

2.8

3.1 2.9

4.7

Example 2

Acetate rayon of 100 to be settled some Amylosealkyläther at 55 ⁰ C in chain form with aqueous solutions.

The results are as follows:

plain

Degree of substitution

Concentration sizing

strain

O/ /O

Smoothness

first time [tenth time seconds

Amylose methyl ether
Amylose ethyl ether.
Amylose propyl ether

0.53 0.23 0.19

9.2 9.2 9.2

Example 3

2 to 7.2
1.6 to 5.8
2 to 5.6

18.6
18.5
18.8

2.9 2.4 3.0

2.6 2.9 3.8

Continuous nylon threads (based on caprolactam) 45 size based on polymethacrylic acid used for

of 100 denier is determined in chain form at 45 ⁰ C with sizing of nylon threads, sizing,

an aqueous solution of an amylose ethyl ether The sized yarn is on drums at 80 to

(Degree of substitution 0.40). Dried 90 ° C for comparison,

will under the same conditions also with a The results are as follows:

plain

Degree of substitution

Concentration sizing

strain

Smoothness

first time

tenth time

Seconds

Amylose ethyl ether.
Polymethacrylic acid

0.40 0.40

This shows that amylose ethyl ether is about as good as that specifically for nylon thread recommended polymethacrylic acid.

Example 4

An oxypropyl ether of amylose, degree of substitution 0.51, a mixed ethyloxypropyl ether of amylose,

9 9 2.8 to 13.2
2.6 to 15

29
26.4

2.4 2.1

2.8 2.3

Degree of substitution 0.18 for the ethyl groups and 0.30 for the Oxyäthylgruppen, both of which are soluble in cold such as in hot water, and gelatin are used for the sizing of the Acetatseideketten 75 at 60 ⁰ C. A small amount of glycerine is added to the gelatin solution.

The following numbers for the sizing are obtained from the yarn investigation.

7th Con-
Zen-
tra-
tion
7o Gluing plain Substitu
degree of movement VO VO VO 2 to 7.0
2.2 to 7.6
2 to 7.2 Amyloseoxypropyl
ether
Amylose ethyloxy
propyl ether
gelatin
(+ Glycerine) 0.51
0.18 + 0.30

Example 5

Cotton Ne 24/1 is guided in chain form at 80 ⁰ C continuously through a 10 ° / ₀ strength of a sizing solution Amyloseäthyläthers (degree of substitution 0.30), pressed and dried on a drum at 110 ⁰ C. For comparison, a sizing test is carried out with a low-boiling starch preparation in the same concentration.

The yarn analysis gives the following results:

plain Con-
Zen-
tra-
tion
% Sub-
stitu-
functional
Degree Frictional
strength fracture
firm
speed
G Deh
tion
° / o No 10
10 0.30 84
1144
352 269
.420
410 7.2
6, L
6th Amylose ethyl
ether
Low boiling point
strength

Example 6

Is pumped in a closed dyeing apparatus for 15 minutes at 5O ⁰ C, an aqueous 4% solution of a Amyloseäthyläthers (degree of substitution 0.26) by a Viskosespinnkuchen.

The sized spider cake is easy to unreel and the yarn has an excellent quality Gluing.

Example 7

A strand of 100 den acetate rayon is kept submerged Amyloseäthyläthers a degree of substitution of 0.23 at 60 ° C for several minutes in an aqueous 9.2 ° / ₀ solution. After pressing and loosening the strand in a dry box at 9O ⁰ C is dried.

It is found that the sizing of the yarn is 1 to 6.8 and the elongation is 25%.

Example 8

Continuous triacetate yarn of 100 den is treated at 50 ° C with an aqueous solution of a water-soluble, mixed ethyl benzyl ether of amylose, which is obtained by making amylose in an alkaline medium in the heat with 0.7 mol of diethyl sulphate and 0.05 mol of benzyl chloride per glucose unit treated and then freed from the reaction salts in a known manner and in dry form brings. For comparison. Is made under the same conditions also with a synthetic polyvinyl alcohol based sizing in the presence of a small amount Amount of boric acid sized. After the treatment, the yarn is dried on a drum at 95 ° C.

The yarn analysis gives the following results:

plain Conc
tration Gluing strain Smoothness
first time tenth time
Seconds 2.2
3.2 Amylose ethyl benzyl ether
Polyvinyl alcohol + 1.6% boric acid 8th
8th 2.8 to 14.4
2.6 to 12.6 26.1
26.2 2.1
2.6

Example 9

That described in Example 8, mixed Äthylbenzyläther of amylose is studied in comparison with the corresponding corn starch ether for sizing the Diacetatseideketten 75 at a temperature of 6O ⁰ C.

The following numbers are obtained for the sizing during the yarn analysis:

plain Conc
tration
° / o Gluing Amylose ethyl benzyl ether
Starch ethyl benzyl ether ... VO VO 1.8 to 9.2
1.1 to 4.2

Example 10

Cotton yarn is continuously immersed in chain form at 8O ⁰ C by a 10% aqueous solution of the sodium salt of a Amylosecarboxymethyläthers, and pressed on a drum at HO ⁰ C dried.

The amylose ether is produced by treating amylose in an alkaline medium in the heat with 1 mol Has treated sodium monochloroacetic acid per unit of glucose, whereupon the treated in this way Amylose is freed from the reaction salts in a known manner and brought into dry form. The degree of substitution of the amylose ether is 0.56 carboxymethyl groups per anhydroglucose unit. For comparison are sizing experiments with the sodium salt of a carboxymethyl ether of cassava starch (degree of substitution 0.59) as well as with the sodium salt of a low-viscosity carboxymethyl cellulose type (degree of substitution 0.6) carried out. The starch ether is obtained by using cassava starch in well-known Way etherified with 1 mol of sodium monochloroacetic acid per glucose unit and the ether thereupon from the Has cleaned reaction salts.

The yarn analysis shows the following results:

plain Con-
Zen-
tra-
tion
° / o Travel
exercise
consolidate
speed fracture
firm
speed
G Deh
tion
% No 10
10
10 87
879
367
551 296
455
381
393 7.5
7.1
6.4
6.6 Carboxymethyl ether of
Amylose (Na-SaIz)
Carboxymethyl ether of
Starch (sodium salt)
Carboxymethyl ether of
Cellulose (sodium salt)

Example 11

A Diacetatseidekette 75 of which one can continuously at 60 ⁰ C by an 8% aqueous solution of Amyloseacetat skid, is squeezed and then the yarn. The water-soluble amylose acetate is obtained by hydrolyzing an amylose triacetate solution in the presence of water and a small amount of catalyst until the amylose acetate has become completely water-soluble.

ίο For comparison, sizing tests are also included water-soluble starch acetate and water-soluble cellulose acetate, which in a corresponding manner from the Triacetates have been performed. The treated yarn is on drums at 80 to 90 ° C dried.

The following results were obtained from the yarn analysis:

plain Conc
tration Gluing strain GIa
first time
sparkling wine diness
tenth time
in the Amylose acetate 8th
8th 2.7 to 9.4
1 to 3.4 17th
12th 1.9
2.7 2.1
5.2 Starch acetate 8th 1.2 to 5.0 15.5 2.4 3.7 Cellulose acetate

Example 12 3 <>

Cotton yarn is aqueous with a 10% igeti Amylose formaldehyde compound solution. The yarn sized in this way leaves process well in the weaving mill.

Example 13

A dry amylose ether which can be used according to the invention has been manufactured as follows:

1000 g of finely ground amylose obtained by fractionating potato starch and a solution of 170 g of sodium hydroxide in 2000 ml of water are ^{stirred in a stirred autoclave at 50 to 60 °} C. to form a smooth dispersion. Then 350 ecm of dimethyl sulfate are added within 45 minutes, whereupon the mass is allowed to react for a further 1 hour at the same temperature. The reaction mixture is then dried in a thin layer on a heated roller at a vapor pressure of 6 atm. The amylose methyl ether obtained is particularly soluble in both cold and hot water. The ether has a degree of substitution of 0.53 and thus contains 1 methyl group per 1.88 anhydroglucose units.

Claims (8)

PATENT CLAIMS: 55 1. A method for sizing textile yarns, characterized in that they are treated with an aqueous solution of an ether, ester or acetal of amylose and the yarn treated in this way is dried. 2. The method according to claim 1, characterized by the use of an aqueous solution of a Alkyl, oxyalkyl or mixed alkyl-oxyalkyl ethers of amylose, in which the alkyl or oxyalkyl groups contain 1 to 4 carbon atoms. 3. The method according to claim 2, characterized in that that the ether has at least 1 alkyl and / or oxyalkyl group per 7 anhydroglucose units contains. 4. The method according to claims 2 and 3, characterized by the use of aqueous Solutions of the alkyl, oxyalkyl or mixed alkyl-oxyalkyl ethers for sizing hydrophobic Yarns. 5. The method according to claim 4, characterized in that the ether is also an aromatic Contains remainder. 6. Process according to Claims 4 and 5, characterized in that one is an oxyalkyl ether applies, which contains at least 1 ether group per 2.5 anhydroglucose units. 7. The method according to claim 1, characterized in that a hydrophobic yarn with a treated aqueous solution of an amylose ester of a fatty acid having 2 to 4 carbon atoms. 8. The method according to claim 1, characterized in that a hydrophilic yarn with a treated aqueous solution of an ether, ester or acetal of amylose, the or that in the substituent a hydrophilic group, preferably a carboxyl, sulfonic acid, amino or substituted one Amino group. Considered publications:
Angewandte Chemie, 63 (1951), pp. 153 to 155;
German patent specifications No. 869 030, 921 440. 109 747/532 11.61