DE939924C - Process for the finishing of textile structures made from regenerated cellulose - Google Patents

Description

The invention relates to a method for refining structures made of regenerated cellulose, such as threads, fibers, fabrics, knitwear.

Fabrics, knitwear or products otherwise made from threads of regenerated cellulose '' show the property of shrinking after repeated washing. In addition, these products have a Wet strength, which is considerably lower than their dry strength. There are already different modes of treatment has been recommended for threads or the structures made from them, with the aim of to eliminate these undesirable properties.

Besides the various improvements in terms of stability, dimensions and properties when wet, obtained as a result of these different treatments, one can often achieve improvements in the related textile properties. These include crease resistance and wear resistance, behavior when worn and similar properties. The ideal treatment is one that produces the most favorable results in terms of use results in important properties, on the other hand does not cause any undesirable side effects. Certain treatments can achieve excellent results with regard to one property, but they are disadvantageous with regard to other properties or they impart undesirable properties to the material.

For regenerated cellulose, especially for those made by the viscose process, "one of the most important problems is that of dimensional stability. It is known to use a glyoxal treatment to make the cellulose shrink-free (US Pat. No. 12,436,076), However, there is a decrease in strength and elongation at break in the dry and in the wet state.This phenomenon is explained by the fact that the cross-bonds between the adjacent cellulose macromolecules are so short that the structure obtained is too rigid. . the invention is now a process for treating cellulose-containing fabrics, wherein the shrinkage tendency of these materials is considerably suppressed while maintaining the physical properties of the treated material are not adversely affected.

The method according to the invention is characterized in that the textile structures are treated in the presence of an organic acid with an aqueous solution of cc-oxyadipinedialdehyde, the terminal carbon atoms of which are separated by 4 carbon atoms, whereupon the structures are at a temperature below the boiling point of water dried and the dried products heated at a temperature above the boiling point of water. Preferably, the aqueous solution contains 4 to 10% of dialdehyde and 0.3 to 1.2 ° / ₀ of organic acid. The oxyadipinedialdehyde is preferably used in a concentration of 8%.

The organic acid used is preferably oxalic acid, and according to a favorable embodiment of the process according to the invention, this acid is used in a concentration of 0.6%. A favorable temperature for drying the treated product is 50 ⁰ , and for heating the dried product a temperature of 110 to 120 ° is preferably used, for a period of 3 to 4 minutes.

The organic acid used serves as a catalyst in the dialdehyde treatment. The α-oxyadipinedialdehyde used has the formula

O OH O

! I I Il

HC _(CH2) ^ - C El · - CH

The solubility of the commercially available product is insufficient to produce solutions with a concentration of 10%; However, this difficulty can be obtained by application of a solvent mixture consisting of _^2/3 of water and ^x / ₃ of dioxane are overcome.

. The process according to the invention is illustrated by the following examples.

example 1

From a spinning cake made from washed, but not yet dried, viscose rayon threads with With a titer of 150 denier and 40 individual threads, strands of 450 m of thread were unwound by hand. Undried material was used for the following two reasons: 1. Undried, regenerated cellulose is still in the gel state and is more reactive than after drying. 2. This is the most appropriate procedure for including the procedure in the Viscose processing course.

Is prepared, a treatment solution having from about 8 ° / ₀ a-Oxyadipindialdehyd and 0.6% oxalic acid by mixing 147 g of 55 ° / _o aqueous solution of the dialdehyde with 300 cm ³ of dioxane and diluting the volume to 1000 cm ³ with water and Addition of 6 g of oxalic acid as a catalyst. The dioxane is added to avoid the formation of a precipitate on dilution with water.

The wet tresses were immersed in this treatment solution for 5 minutes at 50 to 60 ° and then spun off for 5 minutes. It was then dried at 50 to 55 ° for one hour. The dried tresses were then heated for the times and temperatures given below. After heating, the tresses were washed out in a solution containing 0.25% soap and 0.1% Na ₂ CO ₃ at 70 ° and then rinsed until the product was free of soap and alkali; Then they were treated with a 10% emulsion of a softening agent, spun off again and finally dried for one hour at 50 to 55 °. After conditioning, the tresses were applied to bobbins and the dry and wet strength and elongation at break of the threads were measured.

The results were as follows:

Heating Time 4 min. Dry
strength
G properties fracture
strain
in dry
State fracture
strain
in wet
State template Temp. Control ·.
(untreated) 3 min. 177 Wet
strength
G 21.7 30.4 I. 110 ° 199 92 15.6 15.2 2 120 ° 200 HS 17.6 l8.2 3 II9

Example II

Strands of viscose rayon were treated in the same way as in Example I, while the con-

Treatment solution Oxalic acid Dry
strength properties fracture fracture strain
in dry strain
in wet template aldehyde 0 /
/ 0 G Wet
strength State State 0.60 145 % % % 0.23 189 G 14.6 13.4 I. 0 0.30 197 58 17.9 17.9 2 3 o, 45 203 97 17.8 18.6 3 4th 0.60 206 107 16.8 i6.4 4th 6th o, 75 199 109 16.3 16.3 5 8th 114 15. ι 15.0 6th IO 105

concentrations of α-oxyadipinedialdehyde and oxalic acid was changed. The heating lasted 3 minutes and was carried out at 120 °. The results were as follows:

Example III

A number of strands of rayon rayon were treated in the same manner as in Example II, wherein however, this time a heating time of 4 minutes and a temperature of 100 ° were used. The results were as follows:

Treatment solution Oxalic acid Dry
strength properties fracture fracture strain
in dry strain
in wet template aldehyde 0 /
/ 0 G Wet
strength State State O, 6o 158 % % %. 0.23 I ₉ I. G 15.2 13.3 I. 0 0.30 I93 57 i5.4 17.1 2 3 o, 45 188 IO4 15.8 i5.7 3 4th 0.60 202 102 15.1 i5.5 4th 6th o, 75 I98 IO5 15.1 14.5 5 8th II3 15.5 14.6 6th IO IO6

Example IV

A number of tresses were treated in the same manner as in Example I, using a glyoxal treatment solution as compared to an α-oxyadipine dialdehyde solution. The glyoxal solution was prepared according to Examples II, IV and VI of American Patent 2,436,076. The three solutions used contained per liter, 180, 120, and 90 cm ³ of a 3o ° / ₀ by weight glyoxal, and these

Solutions are referred to below as A, B and C, respectively. To make a comparison between the heating ratios in these particular solutions and the To enable the conditions to be used in the α-adipinedialdehyde treatment became one Strand heated according to the ratios given in the American patent and the others were subjected to a heating of 115 ° for 3.5 min. The treatment ratios were no as follows:

template Treatment solution catalyst 0.3% boric acid Heating Time temperature Reagent Control, not treated 0.6% oxalic acid I. A-glyoxal 0.6 ° / ₀ oxalic acid 5 min. 138 ° 2 1.0% oxalic acid B-glyoxal 0.3% boric acid 5 min. 126 ° 3 C-glyoxal 0.6% oxalic acid 5 min. 149 ° 4th A-glyoxal 0.6% oxalic acid 3.5 min. 115 ° 5 1.0% oxalic acid B-glyoxal 0.6% oxalic acid 3.5 min. 115 ° 6th C-glyoxal 3.5 min. 115 ° 7th 8 ° / ₀ adipine dialdehyde 4 min. 110 ° 8th

The results were as follows:

Swelling Dry- Physical properties fracture strength fracture strain template Wet strain in wet % G strength in dry State III 189 State Vo 59 152 G Vo 24.6 I. 6i 163 89 20.9 11.6 2 48 131 84 12.5 14.0 3 98 184 82 15.2 9.1 4th 110 184 72 9.1 18.2 5 102 186. 87 18.8 20.5 6th 77 202 87 19.9 20.8 7th 86 19.8 "14.5 8th 113 "15.1

Example V

A number of tresses were treated with α-oxyadipinedialdehyde in the same way as in Example I. At concentrations of 6 to 8% dialdehyde, oxalic acid concentrations of 0.3, 0.6 and 1.0% were used. Two different heats were applied for each of the variations, namely 4 minutes at iio ° and 3 minutes at 120 ^0th The results were as follows:

concentration acid 0 o, 3% Swelling Dry
strength Physical properties fracture
strain
in wet
State template Dyaldehyde 0.3% o, 3% Vo .: G Wet
strength . fracture
strain
in dry
State % Control,
not treated o, 3%. 0.6% ΙΟΙ 181 G Vo ■ 29.1 I. Heating for 4 minutes at 110 ° 0.6% 0.6% , 89 20.9 8th.% 0.6% 1.0% 98 195 21.9 2 6% r; o% 1.0% 84 199 97 19.6 16.0 3 8th% x.o% 86 203 105 17.0 17.5 4th 6% Heat for 3 minutes at 120 ° 83 202 112 17.0 15.8 5 8th% 6% 83 I99 103 16.8 15.0 6th 6% 8th% 81 I97 106 15.7 14.3 7th 8th% 6% 80 I99 99 16.0 15.0 8th 8th% 103 16.2- 6% 87 194 14.6 9 8th% 91 189 99 16.6 16.4 10 90 I97 109 15.7 14.7 II 81 195 100 16.5 14.1 12th 80 182 ΙΟΙ 15.4 13-4 13th 80 193 9 * 14.8 14.2 14th ΙΟΙ 15.4

Example VI The tresses were treated with an 8% solution of α-oxyadipinedialdehyde, "where oxalic acid,

Adipic acid and succinic acid were used as catalysts. The samples were heated 125 for 4 minutes at 110 °.

The results were as follows:

template

catalyst

Swelling dry strength

Physical Properties

Elongation at break when dry

strength

. G

Elongation at break when wet

I.
2

3
4th
5
6th

control

(untreated)

0.3 7o oxalic acid

0.35% adipic acid .. 0.70 7o adipic acid .. ι, 16 7o adipic acid .. 0.28 7o succinic acid 0.56 7o succinic acid 0.94 7o succinic acid

106 1.98 86 3.44 III 3.33 107 3.25 99 3.30 108 3, i8 98 q.02 110

195

203
191
189

192

191

197
197

97 22.0 28.6 112 i7, o 17.5 94 21.6 25.9 96 21.7 26.6 97 19.2 21.7 91 19.7 22.6 ΙΟΙ 19.5 22.7 ΙΟΙ 20.6 22.9

Example VII

From a viscose artificial silk cake of 150 denier and 40 monofilaments that cleaned well, but not was dried, short lengths of thread were unwound. The specimens were treated with a treatment solution passed through, collected on a metal spool and dried at 50 °.

Three different treatment solutions were used.

A. water;

B. A solution of 87 ₀ a-Oxyadipindialdehyd as in Example I;

C. A glyoxal solution as indicated in Example IV of US ^{Pat. No. 2,436,076, 120 cm 3 of} 307% glyoxalic acid and 6 g of oxalic acid being added to 1000 cm ^{3 of} water.

The treatment solutions were kept at 50 °.

The dried filaments were placed on the metal spool under the proportions given below heated, whereupon their physical properties and residual shrinkage were determined, with the following Results were determined.

Treat Heating Temp. Dry
strength Physical Properties fracture fracture Shrinkage lung strain
in dry strain
in wet template solution 191 State State 4.6% Time 120 ° 207 Wet
strength ii.i7o 17.6% 3.6 7o A. 120 ° 206 10.5 7o 14.6 7o 3.4 ° / o I. B. 126 ° 192 78 9.9 7o 14.8 7o 4.6% 2 B. 3 min. 126 ° 188 102 10.7 7o 17.2 7o 4.2% 3 C. 6 min. IO7 10.7 ° / o i6.4% 4th C. 5 min. 8l 5 8 min. 82

Example VIII Hanks of 150 denier yarn containing 40 single threads were treated, as described in Example I, with a 87o% ^en α-oxyadipinedialdehyde solution. From this yarn a length of tube was knitted between two pieces of untreated normal yarn of the same denier.

An attempt was made to use a corresponding piece of tubing made of yarn treated with glyoxal, according to Example IV, pattern 2, but could not do so because the yarn was too brittle. The latter So material could not be used as a comparison material. The shrinkage numbers of the untreated and the treated yarn were as follows:

template length Shrinkage
Width | Surface 25.0%
I6.5% Untreated
Treated 9.2 7o
4.0% 17.5%
13.0%

Example IX

There was a comparison between an 8% solution of α-oxyadipinedialdehyde and a Glyoxal solution made as prescribed in Example II of American Patent Specification 2,436,076, for the purpose of reducing the shrinkage of a fabric. A viscose rayon silk product was used as the fabric used with the following properties:

Structure 114 X 68,

Width 1150 mm,

Warp 100/60 single threads,

Weft 30/1 spun thread.

Two concentric rectangles were drawn on each of the fabrics in washable ink. Each Piece would then be treated as follows:

a) Washed by hand in a hot, 25 ^sec / ₀ % soap solution, rinsed with hot water and squeezed out the excess water on top

b) submerged at 70 ⁰ and for 15 minutes in the treatment solution and wrung out by hand;

c) the moist material was stretched out on a drying frame to the original dimensions and well dried at 50 ^0;

d) the dry material was removed from the frame and (for the purpose of hardening the aldehyde) heated, on it

e) Washed by hand in a warm solution (50 °) of 0.25% soap and 0.1% Na ^ CO ₃ , thoroughly

rinsed in hot water and dried completely free and tension-free on a horizontal gauze;

f) the shrunk dried fabric was ironed (avoiding any sliding movement of the iron), whereupon the demarcated surfaces are measured at ten points in each direction became. The shrinkage after the first wash was then calculated.

The washing and drying process as well as the measurement, as indicated under e) and f), were repeated a few times repeatedly for the purpose of determining a possibly progressive shrinkage with repeated To wash.

The treatment solutions used under b) and d) and heating conditions were as follows:

tissue

Treatment solution

Control.

Saturated with pure water and dried on frames

120 cm ³ 3O ° / ₀ glyoxal and 6 g of oxalic acid with water -to-i_Xiter- ~ diluted "

147 g of 55 "/ o a-oxyadipinedialdehyde, 6 g of oxalic acid and 300 cm ^{3 of} dioxane diluted with water to one liter

Heating time I temp.

not heated

5 min.

3.5 min.

126 ⁰

115 °

After the last shrinkage measurements, the tensile strength and elongation at break measurements were made in double determination of the warp and the weft of each fabric was carried out. Here specimens were used which had a width of exactly 25 mm. Since the pieces are different had shrunk, they showed a different number of threads / cm, which had to be taken into account when comparing the strength values when considering the wants to recognize the effect of the aldehyde treatment in this regard. Every value for strength was taken therefore evaluated taking into account the number of threads / cm.

The results are shown in the table below.

Shrinkage 7 ,, ¹ )

tissue treatment chain Ablution ι
A shot surface chain Washing 2
A shot surface ⁵⁰ ι
2
3 water
Glyoxal
α-oxyadipinedialdehyde 17.4
9.9
11.2 4.0
3.1
3.1 20.4
12.7
I3.9 16.7
10.4
ii, 7 4.7
2.8
3.4 20.6
12.9
^X 4.7

gg (continued) Washing 3
A shot surface chain Washing 4
A shot surface chain Washing 5
A shot surface chain 4.4
2.8
2.8 20.2
12.9
12.7 18.6
12.0
10.2- 4.7
3.1
'2.8 23.2
14.8
12.7 18.6
10.7
11.2 5.0
3.2
3.4 22.3
13.5
14.2 16.6
⁶⁰ 10.4
10.2

^x ) Calculation based on the original dimensions.

(Continuation)

Strength ² )

According to the experiment chain A shot Calculated on
Original fabric ³ ) A shot chain A shot 22nd 21 chain 29 23 25th 19th I? 57 24 19.5 I8.5 20th 18.5 33 20th 21 21 34

² ) Breaking strength in kilograms for a strip of 2.5 cm.

³ ) Calculated on the basis of the original fabric, taking shrinkage into account.

Example X

A number of pieces were treated in the same way as described in Example IX, only with the Difference that

ι. the material was dried without tension in order to avoid any weakening of the fibers by excessive Elongation required to bring the wet fabric back to its original dimensions would be to avoid;

2. a spin-off was used after the aldehyde treatment, as is the case with the yarn treatment was the case (cf. Example I), the aldehyde content during drying was more than that of the treated yarn to make comparable.

The results are shown in the table below.

tissue

chain Wet A shot Wet Stretching chain Wet A shot Wet Breaking strength ¹ ) 18.4 25.3 Dry 7th Dry 7o Dry 14.8 Dry 12.7 % 46 % 28 51.7 24.0 44.8 22.3 43 24 28 14th 25.4 20.8 30th 31 14th 19th 40.1 35, i 41 20th

1. Control

2. Glyoxal ..

3. dialdehyde

35 ¹ J Corrected for the increase in the number of threads per cm ² due to shrinkage.

The manner in which the dialdehyde is applied to the material can vary widely, but it is advised to manipulate the threads while they are still in the gel state, d. H. in front of any Drying. The inventive method is therefore well suited for application to the German The device described in patent specification 845,686. In this device, the dialdehyde solution can be used with use very good success in the final treatment tube and before drying.

The drying of the treated material is preferably carried out at about 50 ^0th Any excess liquid present is expediently removed mechanically before drying.

It has been found that the heating can take place most advantageously at a temperature between 110 and 120 ^° and for 3 to 4 minutes. Longer heating or a higher temperature leads to a decrease in strength, while insufficient heating does not achieve the maximum strength and the desired shrinkage strength.

The heating time and the temperature are inversely proportional.

In the above examples, the effect of the method according to the invention for treating after Regenerated cellulose produced using the viscose process is highlighted. However, that is limited Invention not on it, and other types of regenerated celluloses, e.g. B. copper oxydammonium rayon, can be improved by this method.

Claims (6)

PATENT CLAIMS: 1. A process for the finishing of textile structures made from regenerated cellulose, characterized in that these structures are treated in the presence of an organic acid with an aqueous solution of α-oxyadipaldehyde, whereupon the structures are ^{dried at a temperature below 100 c} and the dried structures are raised a temperature above 100 ° can be heated. 2. The method according to claim 1, characterized in that the aqueous solution contains 4 to 10 ° / ₀ of the dialdehyde and from 0.3 to 1.2% of an organic acid. 3. The method according to claim 2, characterized in that the aldehyde is used in a concentration of 8 ° / ₀ . 4. The method according to claim 1 to 3, characterized in that the organic acid is oxalic acid, preferably at a concentration of 0.6% is used. 5. The method of claim 1 to 4, characterized in that the drying of the treated text lien structure is carried out at about 50 ^0th 6. The method according to claim 1 to 5, characterized in that the heating of the dried Formation at a temperature between around 120 ° and during 3 to; 4 minutes. Referred publications: Excerpts from German patent applications VoI: 13 from May 11, 1949 (registration J 67258 IVd / 8k).