JPS58174621A - Filament, yarn and fiber based on polyvinyl chloride and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to filaments, yarns, fibers and other similar products comprising at least 70% by weight of ordinary polyvinyl chloride and up to 30% by weight of cellulose acetate.

Fibers based on polyvinyl chloride have certain special properties,
It has value in the textile field, for example, for its nonflammability, negative triboelectricity, photoresistance, and chemical and electrical inertness. However, common polyvinyl chloride produced by the least expensive and therefore most commonly used method, i.e. at temperatures between 0 and 80 °C under the action of heat, mainly It is an atactic polymer with a glass transition temperature 1&(Tg) of the order of 85°C. Therefore, the yarns and fibers obtained from atactic polyvinyl chloride itself, after drawing and stabilization and the yield
Although they previously have mechanical properties suitable for their conversion into textiles, the finished products have excessively high shrinkage rates that can be as high as 30%. If they were subjected to shrinkage treatment at this stage, their mechanical properties would be insufficient to avoid re-stretching during conversion into textiles, resulting in too high a shrinkage ratio making these fibers It becomes impossible to dye at 98° C. according to the general dyeing method.

A method of improving the properties of fibers based on polyvinyl chloride is carried out from vinyl chloride at temperatures below 0°C and down to below -60°C in the presence of suitable catalysts that are effective at these low temperatures. New polymers have been developed using techniques based on polymerization.

These new polymers, which have a predominantly syndiotactic structure, generally have glass transition temperatures (Tg) of 90-100°C or higher, which compare favorably with common polyvinyl chloride-derived textile products. Provides yarns and fibers with heat resistance and considerably improved properties. 1973
French application number 2,161, published on July 6,
084 describes a fiber that is based on this type of polymer and has good mechanical properties. however,
This type of low-temperature polymerization process is a very expensive process, which increases the cost of the fiber considerably and is not advantageous for industrial production.

According to French patent 1,359,178, a method of improving polyvinyl chloride (PVC)-based fibers and yarns by mixing ordinary polyvinyl chloride with post-chlorinated polyvinyl chloride has also been proposed. There is. Although this solution indeed yields yarns and fibers with better mechanical properties, it is also an industrially more expensive solution, the greater the proportion of chlorinated polyvinyl chloride added.

With the addition of a small amount of cellulose acetate, it contains a predominant proportion of pure polyvinyl chloride and combines good mechanical properties, especially good toughness, relatively low elongation and at the same time low residual shrinkage. It has been found that yarns and fibers can be obtained which, after being converted into textiles, can be dyed by a boiling point dyeing process.

Such yarns and fibers can also be obtained in an economical and industrially rapid manner.

More particularly, the invention consists of 70-92% ordinary polyvinyl chloride and 8-30% cellulose acetate, which after shrinkage in boiling water has a shrinkage of at least 20 cN/l.
ex to about 30 cN/1en (7) Relating to filaments, yarns and fibers having a toughness, an elongation at break of less than 6θ% and a residual shrinkage in boiling water of less than 5%.

Generally, they have a toughness of at least 23 cN/len, an elongation at break of less than 50%, a
It has a shrinkage in saturated steam at 05° C. and an absorption capacity according to the DIN standard provisions of more than 50%, generally more than 70%.

The present invention also provides a solution of the polymer having a concentration between 15 and 30% containing 60 to 80% by weight dimethylformamide and 20 to 40% by weight water at a low temperature, preferably 0 to 30%. A yarn containing 8-30% cellulose acetate and 70-9'2% polyvinyl chloride by weight, consisting of spinning in a coagulation bath maintained at a temperature between 20°C and It also relates to a method for producing fibers.

The filament is then subjected to first-order drawing, which is carried out in a medium consisting of water and dimethylformamide at a ratio between 2 and 4x, preferably at a temperature between about 5 and 40°C. washing the filament, generally with water, and drawing the filament again in an inherently corrugated medium at a temperature above 90° C. at a ratio between 2 and 4×, with a total draw ratio between 4 and 1×, sizing; It is then stabilized under tension in an aqueous fluid medium at a temperature above 100°C and then contracted in the free state in an aqueous fluid medium at a temperature above 100°C.

The term "polyvinyl chloride" is to be understood essentially to mean polyvinyl chloride consisting of the atactic isomeric form with a glass transition temperature generally between 65 and 85°C. The polymers are prepared in the least expensive manner by known bulk, suspension or emulsion polymerization techniques, generally at temperatures below 0°C, more typically from 20 to 60°C.
It is most commonly obtained at temperatures of °C or higher.

The term "polyvinyl chloride" refers to compounds containing ethylenic double bonds, such as vinyl acetate, vinyl and (meth)acrylic esters and ethers,
It is to be understood as meaning a polymer containing at least 95% (by weight) of vinyl chloride copolymerized with acrylonitrile and olefins, such as ethylene.

The term "cellulose acetate" refers to both so-called secondary acetates and triacetates, i.e. in fact the degree of substitution of alcohol groups by acetyl groups is 1 per glucose unit.
, 8 to 3 (total acetic acid level between 45.68% and 62.5%).

Surprisingly, the yarns and fibers according to the invention exhibit superior mechanical properties over yarns and fibers derived from each component itself.5. and dimensional stability (,,.

In particular, after shrinkage in boiling water they shrink to at least 2
0 cN/le richness, preferably at least 23 cN/le
1 toughness of x and less than 60%, preferably 50%
having an elongation at break of less than 5%, preferably less than 3%;
Necessary only when coexisting with residual shrinkage in boiling water.

In practice, toughness and elongation values can only have real meaning when combined with residual shrinkage, because before the final shrinkage process these types of properties are relatively This is because, even if it is high, the residual shrinkage is too high to convert the fibers while retaining their advantageous textile properties.

Before the spinning operation, a solution is prepared in the following manner: first a solution of cellulose acetate in dimethylformamide is prepared at room temperature with stirring, and then polyvinyl chloride is added in powder form with vigorous stirring, and the solution is The temperature of is 1
The temperature drops below 0℃.

A solution having a concentration of between 15 and 30%, preferably between 18 and 25%, is first heated to a temperature of 80° C. until dissolution is complete and then spun in a water bath of dimethylformamide, Here, the weight proportions of dimethylformamide and water are 60 to 80% by weight of dimethylformamide and 4% by weight of dimethylformamide and water.
It can be changed between 0 and 20% water, and the coagulation bath is 0 to 2%.
The temperature is maintained between 0°C. By passing the filament initially in a medium consisting generally of water and dimethylformamide in the proportions of 30/70 to 70/30 in a suitable rolling stock or tank at a temperature between about 5 and 40°C. Stretching is carried out at a ratio between 2 and 4x, where the stretching ratio clearly depends on the medium and temperature.

In particular, the higher the stretching ratio, the higher the temperature.

The filament is then generally placed in countercurrent water at ~room temperature.
At a temperature of 60° C., washed and stretched again in an aqueous fluid medium, for example in a boiling water bath or in a tube, to a ratio between 2 and 4x, bringing the total stretching ratio between 4 and IIX. .

After sizing according to the method of Dantsu, the filament is then stabilized under tension in an aqueous fluid medium at temperatures above 100°C, for example by passing it through a bath of boiling water or in pressurized steam. 10 for 1-3 seconds
This can be done by stabilizing at temperatures between 5 and 130°C.

Free shrinkage is carried out in boiling water for various periods of time, such as for at least 10 minutes, preferably 20 minutes.
or in saturated steam, e.g. French Patent No. 83/
329-1.289.491 through a nozzle such as that described in US Pat. In this type of nozzle, the filaments are treated with saturated steam at a temperature between 105 and 130[deg.] C. and at the same time they shrink and pleat, resulting in good subsequent fabricability.

Similarly, if shrinking is carried out in boiling water, it is preferably mechanically shirred beforehand using the same known methods to facilitate subsequent processing.

The yarns and fibers obtained in this way have better mechanical properties than pure polyvinyl chloride fibers and pure cellulose acetate fibers, especially good toughness, relatively low elongation, even at low cellulose acetate proportions. , good residual shrinkage rate,
It has good dimensional stability to heat treatments such that the fibers can be dyed at the boiling point, good dyeing affinity for plasto-soluble dyes and good absorbency, especially in accordance with DIN standard regulation 53,814, which Overall, it's an amazing feature.

All operations beyond dissolution can be carried out continuously and therefore under conditions that are industrially easily obtainable and economically advantageous.

The dissolved polymers spun in accordance with the present application may contain common additives such as stabilizers, fluorescent brighteners, pigments, dyes, and properties such as color, dye affinity, electrical resistance, etc. It can contain a plasticizer that can improve the properties.

By this method, filaments are obtained at advantageous prices which can be subjected to all textile operations suitable for the processing of filaments and which can be used as such or in combination with other yarns for the production of textiles, knits, non-woven products, etc. and they can be subjected to normal washing and dry cleaning under suitable conditions without undergoing subsequent shrinkage.

It should be understood that the examples described are for illustrative purposes only and are not intended to limit the invention, in which parts are by weight.

In the example described below, the tenacity and elongation values are IN5.
It was determined using an apparatus commercially known under the name TRON by determining the maximum force that the sample could withstand against its gauge, and this force was measured at a constant stretching gradient.

χ Seal” Cellulose acetate (acetic acid standard: 54.8% -180~19
1 in dimethylformamide with a degree of polymerization (DP) in the zero digits
A 0% strength solution was prepared over 1.5 hours with stirring at room temperature.

Atactic polyvinyl chloride (900 digit DP),
While stirring vigorously, add to this solution which has been cooled to 5°C.
The solution was added in a basket such that it contained -20% cellulose acetate, based on total polymer weight, and 20% polymer, based on total dissolved acid.

This solution was then heated to 85°C for 1 hour and 3.00°C
The yarn was spun through a spinneret with zero 0.12 mm diameter holes in a coagulation bath kept at 8° C. containing dimethylformamide and water in a weight ratio of 68/32.

The filaments were passed through a water bath kept at 35°C containing 35% dimethylformamide, where they were drawn at a ratio of 3x. After washing in countercurrent water, they were further stretched in a boiling water bath at a ratio of 3x and then sized.

They are then cured under tension for 2 minutes at a temperature of 120 °C in the presence of pressurized steam, and then in a bath of boiling water for 20 minutes.
Deflated for minutes.

The obtained filament had the properties listed in F.

Gauge per strand, dtex 3 toughness, cN
/lex 22 elongation, %
43 Residual shrinkage rate, % (boiling water) 3 Comfort index (DI
N Standard provision 53,814 water retention capacity 1%) 74 Residual shrinkage in saturated steam at 105°C, % 3.51 Residual shrinkage in saturated steam at 15°C, % 7.5 1λ First , a solution of cellulose acetate in dimethylformamide was prepared in the manner described in Example 1, and polyvinyl chloride was then added in the presence of a stabilizer of 3 parts per 1,000 parts (with respect to polymer), Here the total polymer concentration is 20% by weight and the proportion of cellulose acetate is 20% by weight.
%Met.

Dissolution was carried out at 85° C. with stirring for 60 minutes and the solution was poured into 3,000 0.1 diameter
The fibers were spun through a spinneret with 2 mm holes in a coagulation bath kept at 8°C containing 7% dimethylformamide and 30% water.

The filaments were passed through a bath of 35/65 dimethylformamide and wood kept at 35°C, where they were drawn at a ratio of 3x. After washing in free flowing water, they were further stretched in a boiling water bath at a ratio of 3x and then sized. They were then cured under tension for 2 minutes at a temperature of 120°C in the presence of pressurized steam and then shrunk for 20 minutes in a bath of boiling water at 100°C.

The filament obtained had the following properties:

Gauge per strand, dtei 2, 60
Toughness, cH/lex 23 elongation,
% 43.5 Residual shrinkage, % (boiling water) 3 Comfort index (D
Water holding capacity according to IN standard provision 53.814, %) 63 Residual shrinkage in saturated steam at 105 °C, % 3.5 Patent applicant
Robyal Agent Patent Attorney Hei Odajima 8

Claims (2)

[Claims] 1. Atactic polyvinyl chloride having a glass transition temperature between 65 and 85°C containing at least 95% vinyl chloride groups of 70-92% atactic acid, and 8-3
Consisting of cellulose acetate with 1.8 to 3 acetyl groups per 1 glucose group of 0 weight % and a toughness of at least 20 cN/lex after shrinkage in boiling water, at breakage of less than 60% Filaments, yarns and fibers having elongation and residual shrinkage in continuous water of less than 5%. 2. A solution of the polymer with a concentration between 15 and 30% is kept at a temperature between 0 and 15 °C, consisting of water and dimethylformamide in a weight proportion between 60/80 and 20/40. Spun in coagulation mode. The filament is drawn in a medium of water and dimethylformamide at a ratio between 2 and 4x, washed and the filament is drawn again at a ratio between 2 and 4x in an aqueous fluid medium at a temperature above 90°C. The total draw ratio is between 6 and IIX, the filaments are sized and they are stabilized under tension in an aqueous fluid medium at temperatures above 100°C, and finally the filaments are subjected to an aqueous fluid medium in the free state. It consists of shrinking at a temperature of 100° C. or higher. A method for producing filaments, yarns and fibers according to claim 1.