JPS58174620A - 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 articles comprising at least 75% by weight of conventional polyvinyl chloride and up to 25% by weight of acrylic polymers.

Fibers based on polyvinyl chloride have certain special properties,
e.g. non-flammable, negative triboelectric, photoresistive, chemically inert as well as thermal, acoustic
It is valuable in the textile field for its electrical insulation properties.

However, ordinary polyvinyl 14ide produced by the most inexpensive method, i.e. at temperatures between 0 and 80 °C under the action of heat, is , is an atactic polymer having a glass transition temperature (T g ) of the order of 65-85°C. Therefore, the yarns and ams obtained from atactic polyvinyl chloride itself have mechanical properties that are suitable for their conversion into textiles after stretching and resting, 'after death and before shrinkage. However, the finished products exhibit excessively high shrinkage rates, which can be as high as 30%, and if they are subjected to shrinkage treatment at this stage, their mechanical properties may inhibit PGM elongation during conversion into textiles. As a result, the shrinkage rate becomes too thick and these aiIl
fibers "at the boiling point", i.e. 98°C by common dyeing methods.
So, it becomes impossible to dye.

Improving the properties of fibers based on polyvinyl chloride [1] The use of suitable catalysts which are effective at these low temperatures to improve the properties of polyvinyl chloride-based fibers at temperatures below 0°C and up to 100° above -60°C New polymers have been developed by techniques based on polymerization carried out in the presence of organic matter.

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. It produces yarns and fibers with heat resistance and considerably improved properties. 1973
French application number 2,181, 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 price of the fibers considerably and is not very advantageous for industrial production.

In order to improve the solubility of syndiotactic polyvinyl chloride, attempts have been made to mix it with 5-50% by weight of polyacrylonitrile to obtain a solution that is stable at high temperatures. However, this type of mixture did not solve the cost problem of syndiotactic polyvinyl chloride.

According to French Patent No. 1.359, 178, a method for improving fibers and yarns based on polyvinyl chloride (PVC) by mixing clean polyvinyl chloride with post-chlorinated polyvinyl chloride is also proposed. ing. This solution does indeed give yarns and fibers with better mechanical properties, but the solution is industrially more expensive as the proportion of post-chlorinated polyvinyl chloride is added. There is also.

A predominant proportion of ordinary polyvinyl chloride can be obtained by adding a low V acrylic polymer to plain polyvinyl chloride by standard commercial methods, i.e. under favorable commercial conditions. It is possible to obtain yarns and fibers which contain and have good mechanical properties, in particular good toughness, non-excessive elongation, low residual shrinkage and good dimensional stability. found that dyeing can be carried out by a dyeing method at the boiling point.

More particularly, the present invention comprises 75-92% ordinary polyvinyl chloride and 8-25% acrylic polymer, which after shrinkage in boiling water has a shrinkage of at least 20 cN/
1ex - about 38 cortex toughness (tenaci
ty), elongation at break of less than 60%) and residual shrinkage in boiling water of less than 5%.

Specifically, the toughness is at least 25 cortex, the elongation at break is less than 50%, and the shrinkage in saturated steam at 105° C. is less than 10%.

The invention also provides between 15 and 30%, preferably between 4 and 20
A solution of the polymer with a concentration between 25% and 9%
0-1 consisting of 0% dimethylformamide and 35-10% water, preferably 75-90% dimethylformamide and 25-10% water.
Spinning in a coagulation bath maintained at a temperature between 5°C, the filaments are spun in a water/dimethylformamide medium at a ratio between 2 and 4x, preferably at a temperature between 20 and 50°C. Draw, wash the filament and draw the filament again in an aqueous fluid medium at >90°C/UIR with a ratio between 3 and 5x, total drawing tt wo 6~
IOX, then size the filaments, and strain them to 100% in an aqueous fluid medium.
75-92% by weight, consisting of a stabilization treatment at a temperature below 100°C and finally shrinking the filament in the free state in an aqueous medium at a temperature below 100°C.
It also relates to a method for producing yarns and fibers based on polyvinyl chloride and 8 to 25 ton ψ% of acrylic polymer.・□ t^ "?1 piece of polyvinyl chloride" is 1, which has a glass transition temperature of 4i, generally between 65 and 85 degrees Celsius, in terms of wood quality.
is to be understood as meaning polyvinyl chloride consisting of the atactic isomeric form. Polymers of this type can be prepared in the least expensive way by known bulk, suspension or emulsion polymerization techniques, generally with a polymerization of less than 0i''-, more commonly 2
It is most commonly obtained at temperatures from 0 to 60°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% vinyl chloride copolymerized with acrylonitrile and olefins, such as ethylene.

The term "acrylic polymer" refers to units derived from at least 85% by weight of acrylonitrile and one or more ethylene-based adherents copolymerizable with up to 15% by weight of acrylonitrile, such as vinyl-based compounds; For example, vinyl chloride, acrylic or methacrylic acid, acid esters and acid amides, methacrylonitrile, compounds containing carboxylic acid groups, such as itaconic acid, or sulfonic acid-based compounds 1, such as vinyl sulfone compounds, allyl Sulfonic acids and methallylsulfonic acids, sulfonated aromatic derivatives, styrenesulfonic acid and vinyloxyalenesulfonic acids, vinyl derivatives in basic form 1, such as vinylpyridine and its alkylated derivatives, It should be understood to mean polymers containing vinyl dialkylamine ethers, etc.

The filaments, yarns and fibers according to the invention retain the advantageous properties of polyvinyl chloride, in particular non-flammability and insulation, while surprisingly employing less than 25% t' of acrylic cladding. Even the cases have very favorable mechanical properties, and after shrinkage in boiling water they are at least 20 cN/lea, preferably at least 2
5 cN/lex, toughness and less than 60%,
preferably has an elongation at break of less than 50%, and these two properties preferably have an elongation at break of less than 5%, preferably less than 2%.
It is only significant when coexisting with a smaller residual shrinkage in boiling water.

Furthermore, the yarns and fibers also have dimensional stability in water vapor at 105 DEG C. such that their residual shrinkage is less than 7%.

The yarns and fibers according to the invention are obtained in the following way: The two polymers are first added in the desired proportions in dimethylformamide in the cold, and then the solution is stirred and brought to a temperature of at least 80°C. Heat to bring the polymer concentration of the solution to between 15 and 30%, preferably between 20 and 25%. The solution thus obtained consists of 65-90% by weight of dimethylformamide and 35-10% by weight of water, generally between 0-15°C, preferably between 5-10°C. The yarn is spun in a coagulation bath maintained at a constant temperature.

Next, the filament is generally 30 to 70,000゛ψ.
% to 70 to 30 v-% of water and dimethylformamide, preferably at a temperature between 10 and 50° C., by passing through a suitable roller or tank. It is stretched at a ratio between 4x, the higher the stretching ratio, the higher the temperature, and then washed, generally in countercurrent water. During washing, they may undergo a small controlled contraction simply by adjusting the rollers. The filament is drawn again in an aqueous fluid medium at a temperature of at least 90° C., preferably in a boiling water bath, optionally in a tube, to a ratio between 3 and 5× and then sized by the method of Yuzu. do.

They are then stabilized at temperatures above 100°C in an aqueous fluid medium under tension, either by passing through a bath of boiling water or in pressurized steam.
This can be done by stabilizing in warm IW between 105-130° C. for 3 seconds.

The filament is then shrunk in an aqueous medium at a temperature between 98<0>C and 13<0>C.

Free shrinkage can be carried out in boiling water for various periods, e.g. for at least 10 minutes, generally 10-20 minutes, or in saturated steam, e.g.
3/329-1,289,491 through a nozzle such as that described in US Pat.

In this type of nozzle, the filament is 105-130
Treated with saturated steam at a temperature between 0.9 °C and at the same time they shrink and pleat, which provides good subsequent textile processability. Similarly, if shrinkage is carried out in boiling water, this is preferably preceded by mechanical pleating using known methods for the same purpose to facilitate subsequent processing.

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

The fused composites 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. They can be washed and dry cleaned under suitable conditions without undergoing subsequent shrinkage.

It should be understood that the examples given here are for illustrative purposes only and are not intended to limit the invention, and that the numbers here refer to silicic acid.

In the example described above, the tenacity and elongation values are lN5T.
It was determined using an apparatus commercially known under the name RON by determining the maximum force that the sample could withstand against its gauge, and this force was measured at a constant stretching gradient.

111 A-First, 91.4% of the 4-weight part of 7-acrylonitrile, 7.75% by weight of methyl methacrylate and 0
．． 85i (a copolymer consisting of 11% sodium methallylsulfonate) was added to 1 and then 16 parts of atactic polyvinyl chloride in dimethylformamide kept at about 5°C. The solution was then heated to 85°C and passed through a spinneret with 2°750 orifices to give a solution with a total polymer concentration of 85% dimethylformamide and 15% vocal acid.
The yarn was spun in a coagulation bath maintained at 8° C. containing water. The filaments were passed into a second tank kept at 35°C containing 35% by weight dimethylformamide and 65% by weight water, where they underwent drawing at a ratio of 3x. After washing in countercurrent water, they were further stretched at a ratio of 3x in a tank of boiling water and then sized.

They were then cured under tension in the presence of pressurized steam at 120° C. for 2 minutes, followed by shrinkage in a boiling water bath for 20 minutes. The properties of the obtained filament are summarized in the table below.

A solution of pure atactic polyvinyl chloride with a concentration of 20% hydrogen acid was prepared and spun using the method described in B-)-. The resulting filament was then processed in the manner shown in A.

The properties of the obtained filaments are summarized in Table 6.

Toughness, cN/le! 28 18 growth,%
50 60 Residual Shrinkage, %l.) <5 <5 Gauge per strand, dtex 2.0 2,0
Residual shrinkage in saturated steam at 105°C, % 8 24 JILE First, 2 parts by weight of 91.4 weight % 7crylonitrile, 7.75 weight 1% methyl methacrylate and 0.8
A copolymer consisting of 5% by weight of sodium methallylsulfonate and then 18 parts of 7-tagged polyvinyl chloride were added to dimethylformamide kept at about 5°C to form a copolymer of 20% by weight of sodium methallylsulfonate. A solution with total polymer concentration was obtained. This solution was then heated to 85°C and 2°7
The yarn was spun through a spinneret with 50 orifices in a coagulation bath maintained at 8°C containing 85% dimethylformamide and 15% water.

The filaments are passed into a second tank kept at 35°C containing 35% dimethylformamide and 65% water, where they are mixed with a 7″- I received it. They were then washed in countercurrent water at room temperature, then further stretched in a boiling water bath at a ratio of 3.52X, and then sized. They were cured in a boiling water bath at tension F and then shrunk again in a boiling water bath for 20 minutes.

The filament obtained had the following properties.

Toughness, cN/len 21 Elongation, %
55 Residual shrinkage 1% (boiling water) <5 Gauge per strand, dtex 1, 631
Residual shrinkage rate in saturated steam at 05°C, % 10 Patent - Applicant Robir Attorney Patent Attorney J - Taira Odashima 12

Claims (2)

[Claims] 1.75-92% of atactic polyvinyl chloride with a glass transition temperature between 65-85°C and 8-2%
consisting of a polymer having acrylonitrile units of at least 85 (edge %) of 5@d%, and having a residual shrinkage in boiling water of less than 5% after shrinkage in boiling water, a toughness of at least 20 cN/len, and Having an elongation at break of less than 60%. Filaments, yarns and S fibers. 2. A solution of the polymer having a concentration between 15 and 30% is mixed with 65-90% dimethylformamide and 10-90% dimethylformamide.
Spun in a coagulation bath maintained at a temperature between 0 and 15°C consisting of 35% water by weight, the filaments are drawn in a medium of water and dimethylformamide at a ratio between 2 and 4x and washed. and again draw the filaments in an aqueous fluid medium at a temperature above 90° C. with a ratio between 3 and 5×, the total draw ratio being between 6 and IOX, size the filaments, and place them under tension. 1 in aqueous fluid medium
Stabilization treatment at temperatures above 00°C and finally the filament is stabilized in the free state for at least 1 hour in an aqueous medium.
A method for producing filaments, yarns and fibers according to claim 1, which comprises shrinking at a temperature of 0.000C.