DE1117817B - Process for the production of threads or staple fibers from regenerated cellulose - Google Patents

Description

Threads or staple fibers made from regenerated cellulose, which have been shrinked (e.g. moistened) It is known to pucker spontaneously in a tension-free state.

Various properties of the threads or staple fibers, produced according to the known methods, which can be puckered by a shrink treatment in a tension-free state however, there is still a lot to be desired. Their strength and degree of crimp (number of crimps per Centimeters) relatively small. Also the ripple energy (the energy used to remove the Crimp of a single fiber per unit length is required) of these fibers is low.

The threads or staple fibers made of regenerated cellulose according to the invention have opposite these, produced according to the known processes, significantly higher strength, degree of curling and Ripple energy.

Thus, the number of crimps that arise spontaneously in that the threads or staple fibers, obtained in the process according to the invention, are subjected to a shrink treatment in a tension-free state, is at least 77 =, where d denotes the denier

| / 2 d

represents the degree of thread or staple fiber.

In other words, the latent degree of curling of the original, i.e. not in a tension-free state moistened threads or staple fibers according to

100 ο

of the invention is at least - ^ =.

1/2 d

The threads or staple fibers according to the invention

with a latent degree of curl of at least 1 on
TT = and a high strength in a conditioned process for the production of threads
or regenerated cellulose staple fibers

Applicant:

Algemene Kunstzijde Unie NV,
Arnhem (Netherlands)

Representative: Dr. K. Schwarzhans, patent attorney,
Munich 19, Romanplatz 9

Claimed priority:
V. St. v. America January 29, 1957

Charles Leroy Henry, Chandler, N.C. (V. St. Α.) Has been named as the inventor

State (3 to 4 g / den) are produced by processing viscose in the presence of modifiers in spun in a sulfuric acid spinning bath, which contains sodium sulfate and zinc sulfate, and which are fresh stretched spun products, the viscose and / or the bath 0.02 to 0.2 percent by weight Have modifying agents. The method is characterized in that the ratio of the Percentage of alkali (given in percent by weight NaOH) in the viscose to the percentages by weight of the spin bath components is such that

[Weight percent alkali in viscose (calculated as NaOH)] ²

[Weight percent H ₂ SO ₄ - 0.35 (weight percent Na ₈ SO ₄ - 18.0) + 0.6 (weight percent Zn SO ₄ -4.0)]

where K is at least 7.5.

The spinning of a viscose in the presence of modifiers in a sulfuric acid Spinning bath containing sodium sulfate and zinc sulfate and drawing the freshly spun product are known per se.

The upper limit of K in the above formula is determined by economic considerations in a particular process. The optimal value of K can be determined by experiment.

The usefulness of the formula is explained using the following cases.

Threads made by spinning a viscose containing 5.6 percent by weight alkali in a spinning bath containing 4.5 percent by weight sulfuric acid, 18 percent by weight sodium sulfate, 4.0 percent by weight zinc sulfate and then drawing the freshly spun threads do not have the desired curling properties. Here K had a value of 7.

However, if the same viscose is spun in a spinning bath of the same composition in which but the sulfuric acid content is 4.0 percent by weight

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3 4

the threads have good latent crimping cyclohexylamine, triethanolamine or polyethylene properties (K = 7.8). glycol with a molecular weight of about 4000

On the other hand, threads with the desired ones are used.

Crimp properties are not obtained if the stretching of the freshly spun products,

same viscose is spun in a spinning bath, 5 after leaving the spinning bath, can on

the 4.0 percent by weight sulfuric acid, 16.0 percent by weight can be done in any known manner. Preferably be

percent sodium sulphate and 4.0 percent by weight zinc - they can be reduced by 50 to 100% in a hot second bath.

Sulphate (K = 6.7) contains stretches, whose degree of acidity is lower than the degree of acidity

Although in general the firmness, the frizzy of the spinning bath is.

The degree of curl and the crimp energy of the invention according to the method according to the invention Products are relatively high, threads can be put under tension after drying however, higher values can be achieved if the is not crimped. However, spontaneous frizz viscose occurs in it 5 to 7 percent by weight alkali and the treatment, if afterwards in a tension-free state Spinning bath 16 to 24 percent by weight sodium sulfate are moistened. When she then goes back under and contains 2.5 to 5.0 weight percent zinc sulfate. 15 voltage are dried, the disappears

Examples of compounds that act as modifying crimps but that are after wetting the products

means that have already been applied are, among other things, spontaneously returning in a tension-free state.

Polyglycol ethers or their reaction products with As the crimping only occurs through moistening in

Certain amines, alcohols, fatty acids or a tension-free state cannot occur

aromatic acids, certain aliphatic or crimped threads according to the invention without difficulty

aromatic acids, certain aliphatic acids or in the knitwear industry, weaving and

aromatic monoamines, diamines or polyamines, carpet industry are processed. In case of

certain quaternary ammonium compounds or use of the filaments with latent crimp

heterocyclic bases or certain monocarbami- properties in the manufacture of carpets

nate or dithiocarbamates. 25 then let the piling of the pile take place,

Those made according to known methods by moistening the carpet.

Products, whereby viscose in a sulfuric acid- The crimp energy of the according to the invention

containing spinning bath in the presence of a modification according to a process produced threads amounts to

is spun by means of high strength moistening in the tension-free state 10.0 or

and over its entire cross-section the well-known 30 more milligrams and the curling energy of the

homogeneous skin structure. As a result of these homogeneous threads, which in the same way, but in the absence

Skin structure, these products have no tendency to use a modifier, 5 milli-

for curling up when in tension-free gram.

State to be moistened. The crimping energy is thereby according to the

It must therefore be regarded as surprising. 35 Alexander Brown in "Textile Research Journal"

be determined that in the method according to the invention despite the method described in (12-55),
the presence of a modifier threads and

Staple fibers are obtained which, in their cross-section, Example I
do not have a homogeneous structure. As a result of her

inhomogeneous structure they also puckered 40 Three viscose fabrics A, B and C were made on the following

spontaneously when moistened. Although they are not produced in a homogeneous way.

Structure, their strength is nevertheless matured alkali cellulose in crumb form has been made with

relatively high. 36 ° / ₀ carbon disulfide (calculated on the cellulose)

In the process according to the invention, the mode can be sulfided. The obtained cellulose xanthate was

fixing agent in any stage of 45 at 18 ° C dissolved to a viscose, the 7.5 weight

Viscose production are added. The spinning percent cellulose, 6.9 percent by weight alkali (

bath may contain the modifier, while calculated as Na O H) and 2.25 percent by weight sulfur

it is also possible that both the viscose contained that.

Spinning bath contains the modifier. The viscoses B and C were

The amount of modifier in the viscose 50 dissolves as a modifier 0.3 percent by weight

and / or in the spinning bath is not particularly critical. (calculated on the cellulose in the viscose) des

However, this depends on the compound, the condensation product of di- and tetrahydro-

is used as a modifier. abietic acid and 20 moles of ethylene oxide were added. Of the

In general, an amount of 0.2 to viscose A is sufficient. No modifier was added.

2.0 weight percent in the viscose or 0.02 to 55%. The viscose was then filtered, deaerated and

2.0 percent by weight in the spinning bath. Matured to a maturity of 12 to 18 ° Hottenroth. the

Products with particularly good properties are viscosity of the viscose was 40 to 60 seconds

obtained when using the (falling ball test) as a modifier.

Condensation product of di- and tetrahydro- These viscoses became threads with a titer

abietic acid and 20 moles of ethylene oxide, a compound 60 of 1,300 den and consisting of 720 individual threads

spun the formula.

The spinning bath contained 5.75 percent by weight sulfuric acid and 18.0 percent by weight sodium sulfate

R — n:

CH;

'(CH ₂ CH ₂ O) ^ H

Cl and 4.0 weight percent zinc sulfate while its

65 temperature was 70 ^° C. The spinning length of the threads in the spinning bath was 25 cm.

The spinning bath, in which the viscose A containing no modifier in which R is the radical of coconut oil and χ + y = 15, was spun contained

also no modifier. This experiment served as a control experiment.

The spinning bath in which the viscose B was spun contained no modifier, while the spinning bath in which the viscose C was spun, 600 mg / kg of the compound of the formula

R-N.

(CH ₂ CH ₂ O) ^ H

CH

(CH ₂ CH ₂ O) ^ H

Cl

in which formula R was the radical of coconut oil and χ + y had an average value of 2, was added.

After leaving the spinning bath, the threads were in a second bath at 90 ° C, which is 2 to 3 percent by weight Containing sulfuric acid, stretched by 90%. The drawn threads were with a Speed of 50 m / min, wound on a bobbin, then washed acid-free and dried.

Some of the dried threads were twisted into a thread of 118 turns per meter, from which the strength was then determined in the conditioned and wet state. The conditioned one The condition of the threads was achieved by keeping them at a relative temperature for at least 3 hours Humidity of 60% and a temperature of 24 ° C were kept.

Another part of the threads was immersed in a tension-free state in water of 65 ° C and then dried in a tension-free state.

The number of crimps per centimeter and the crimp energy were measured on conditioned filaments certainly.

The properties of the threads are given in Table I.

Table I

In an attempt at which under the same In some circumstances, the same procedure as for viscose C, but with the spinning bath 200 and 400 mg / kg des Containing modifier instead of 600 mg / kg, it was found that the properties of the Threads were also better than those of the threads mentioned under A in Table I.

Example II

ίο Two viscose D and E were prepared in the manner indicated in Example I. No modifier was added to these viscoses during dissolution.
The viscose was spun in the manner indicated in Example I.

The spinning bath in which the viscose D was spun contained no modifier, while the spinning bath in which the viscose E was spun, 600 mg / kg of a compound of the formula

R-

■ n:

CH.

, (CH ₂ CH ₂ O) ^ H

(CH ₂ CH ₂ O) ^ H

he

in which R was the radical of coconut oil and χ + y = 2 was added. The results are given in Table II.

Table II

Modifier in viscose,% modifier in the spinning bath,

mg / kg

Secondary swelling, ° / o

Conditioned filament strength, g / 100 den

Modifier in viscose,

Spinning bath modifier, mg / kg

Secondary swelling,%

Strength of conditioned threads,

g / 100 den

Elongation of conditioned threads,

Wet strength, g / 100 den ..

Wet elongation, ° / ₀

Number of crimps per

2.54 cm

Ripple energy,

milligram

A. B. 0 0 ^ 3 0 0 80 80 299 337 0.6 9.4 193 189 18.8 18.1 90 115 5.6 13.4

0.3

600 79

336

9.7 198 18.3

120 15.6

Elongation of conditioned threads,%

Wet strength, g / 100 den

Wet elongation,%

Number of crimps per 2.54 cm .. crimp energy, milligrams ...

0 80

299

9.6 193 18.8 90 5.6

600 79

334

9.6 181

From this table it can be seen that the threads in a spinning bath containing a modifying agent are spun, a higher strength in the conditioned state and a higher crimp energy than the threads spun in a spinning bath without modifying agents.

When viscose E was spun in the same spinning bath, but 200 or 1200 mg / kg des Containing modifying agent, threads with better properties were also obtained.

From this table it can be clearly seen that through the presence of a modifier, the strength in the conditioned state, the degree of curl and the curl energy is significantly higher than in the absence of this agent.

When viewed under the microscope, the threads made from viscose B and C had a core and a skin the skin was not the same thickness everywhere.

Example III

Four viscoses were made in a manner as described in Example I. The viscose contained 1.0 percent by weight of the compound of formula

R-N.

(CH ₂ CH ₂ O) ^ H

CH.

(CH ₂ CH ₂ O) ^ H

CF

in which R was the radical of coconut oil and χ + y

had an average value of 15. The cellulose content of these viscose was 7.5 percent by weight. The alkali content of these viscoses was 6.5, 6.0, 5.5 and 5.0 percent by weight, respectively, calculated as NaOH.

The viscose was spun into threads with a titer of 1300 den and consisting of 720 individual threads as in Example I. The spinning bath contained 18 percent by weight sodium sulfate, 4.0 percent by weight Zinc sulfate and various percentages of sulfuric acid so that

(% Na OH) ²
° / o H ₂ SO ₄

and 7.0, 7.5, 9.0, 9.5 and 10.5, respectively.

From Table III A it can be seen that regardless of the alkali content of the viscose there is a maximum number Crimps per centimeter is obtained, though

Table III A.

7.0 7.5 CVo NaOH) ² 9.0 ι 15th 85 80 75 120 115 Viscose alkali ° / o H ₂ SO ₄ 9.5 I 10.5 30th 50 105 115 - - 8.0 Number of crimps per 2.54 cm 30th 85 - 130 - % 30th 80 6.5 6.0 5.5 5.0

( ⁰ Z ₀ NaOH) ²
«/" H ₂ SO ₄ "

20th

> 7.5

is. The strength in the conditioned state of the threads varied from 325 to 380 g / 100 den.

Another viscose containing 7.5 percent by weight cellulose and 6.9 percent by weight alkali, was spun in a spinning bath, in which the sodium sulfate content of 16 to 24 percent by weight and the zinc sulfate content was varied from 3 to 5 percent by weight.

Here, the maximum sulfuric acid concentrations in the spinning bath were determined at which still Filaments with latent crimp properties could be obtained. These maximum sulfuric acid concentrations were with the appropriate concentrations of salts in the spinning bath and alkali in the Viscose substituted in the formula

[Weight percent alkali in viscose (calculated as NaOH)] ²

[Weight percent H ₂ SO ₄ -0.35 (weight percent Na ₂ SO ₄ -18.0) + 0.6 (weight percent Zn SO ₄ -4.0)]

The calculated values for K are mentioned in Table IIIB. The fact that K is constant shows the validity of the formula as a means of describing the relationship between the alkali content of the viscose and the composition of the spinning bath.

The formula determines the maximum concentration of sulfuric acid in the spinning bath very specifically, well crimped threads are obtained. The optimal sulfuric acid concentration is natural a bit lower.

Table III B

ZnSO ₄ ί 3.0 1 5.0 1 Na ₂ SO ₄ Maximum allowed H ₂ SO ₄ K ί 16 6.3 7.5 4.0 y 20th 7.6 7.6 1 24 9.0 7.6 ί 16 5.6 7.6 20th 7.0 7.6 24 8.4 7.6 16 4.9 7.6 20th 6.4 7.6 24 7.8 7.6

Claims (1)

PATENT CLAIM: 55 Process for the production of threads or staple fibers from regenerated cellulose by spinning a viscose in the presence of compounds such as polyglycol ethers or their reaction products with certain amines, also alcohols, fatty acids or aromatic acids, certain quaternary ammonium compounds, etc., in a spinning bath containing sulfuric acid, sodium sulfate and Contains zinc sulfate, and drawing the freshly spun threads, the viscose and / or the bath having modifiers, characterized in that the ratio of the percentage of alkali in the viscose (given in percent by weight of NaOH) to the percentages by weight of the spinning bath components is such that [Weight percent alkali in viscose (calculated as NaOH)] ² [Weight percent H ₂ SO ₄ -0.35 (weight percent Na ₂ SO ₄ -18.0) + 0.6 (weight percent Zn SO ₄ -4.0)] wherein K is at least 7.5. © 109 740/530 11.61