CA1211581A - Fibers and yarns made from a poly(vinyl chloride) and cellulose acetate mixture; process for preparing the same - Google Patents

Abstract

The present invention relates to filaments, threads or fibers, consisting of 70 to 92% by weight of polyvinyl chloride or of a vinyl chloride copolymer containing at least 95% by weight of vinyl chloride, and 8 to 30% by weight. weight of secondary cellulose acetate having an acetic acid content of 51.63 to 58.60% and the process for obtaining them. Said yarns and fibers have, after retraction in boiling water, a toughness of at least 20 cN / tex, preferably at least 23 cN / tex, an elongation of less than 60%, preferably of less than 50%, a power absorption of at least 50%, preferably at least 70%, and a shrinkage in boiling water and in steam at 105.degree.C less than 5%. They are obtained by wet spinning, double drawing, stabilization under tension and free retraction. The yarns and fibers according to the invention can in particular be used for the production of fabrics or knits, capable of being dyed in broth.

Description

DT hilum ]

The present invention relates to filament, fiber son and other synthetic articles made of plastic made up of at least minus 70 Z9 by weight of ordinary polyvinyl chloride and ~ up to 30% by weight cellulose acetate.
Polyvinyl chloride fibers are popular in the textile sector due to certain particular properties proud such as noninflammabilit ~, negative triboelectricity, regis-light, chemical and electrical inertia. However, the ordinary polyvinyl chloride prepared by Delon the most process commonly used, i.e. hot, at temperatures included between 0 and QUE, because the least expensive is a pre-tactical finance with a transition temperature of the second order T order of order QUE therefore yarns and fibers obtained from tactical polyvinyl chloride alone have after (stretching and fixing - but miserly retraction of the mica qualities -sufficient for their textile transformation but the articles completed have too high a withdrawal rate of up to Up to y Z; if they are treated at this stage with retraction, they then have insufficient mechanical qualities to avoid re-stretching during textile processing, which results in too much shrinkage to be able to dye these "broth" fibers, that is to say according to a dyeing process THAN.
In order to improve the properties of fibers based on y polyvinyl chloride, 8 new polymers have been developed from vinyl chloride by a technique based on a polymerization performed at temperatures below 3 OC and down to -6DC or even lower, in the presence of cota-suitable readers effective at these low temperatures.
These new polymers with predominantly syndic-tactics have a second order transition temperature (T) generally greater than 90 - ~ 00 C giving the wires and fibers obtained better thermal resistance and pro-pieties markedly improved compared to textile products from ordinary polyvinyl chloride. Frank demand silent born 2 161 084 published on 07/07/1973 illustrates fibers good mechanical properties based on this type of polymer.
However, such a low temperature polymerization process is an extremely expensive process which increases considerably-the cost price of the fibers and removes a lot of information keep quiet about their industrial production.
one also proposed, according to the French patent 1,359,178 to improve polychloride-based fibers and yarns vinyl (PIC) by mixing ordinary polyvinyl chloride with polyvinyl chloride on chlorinated. This solution which actually allows better yarns and fibers mechanical characteristics is also a solution all the more more expensive industrially, than the proportion of polychlo-vinyl rush on chlorine added is important.
It has now been found that it was possible to obtain yarns and fibers containing a major proportion ordinary polyvinyl chloride laughter with good mechanical characteristics, especially both good toughness, low elongation and low shrinkage rate residual, allowing after textile transformation dyeing to the broth of such yarns and fibers, by adding a quant minority feel of cellulose acetate. Such sons and fibers can also be obtained by a continuous process economic and industrial.
More particularly, the present invention identifies filaments, threads, fibers consisting of 70 to 92 ~ in weight of polyvinyl chloride or chloride copolymer of vinyl containing at least 95% by weight of chloride of vi-nyle, and 8 to 30% by weight of secondary cellulose acetate having an acetic acid content of 51.63 to 58.60%, and Gold fa -having, after shrinking in boiling water, a tenacity at least 20 cN / tex, an elongation of less than 60%, _ Sri had a lower fine line withdrawal rate in boiling water 5 y.
In general, they have a tenacity of at least 23 cN / tex, an elongation less than 50 y, a st ~ blllt: é dimensional dan saturated steam at QUE inf ~ rleure 5 Z0 and a power absorption of Delon, the DON standard greater than Su%, generally sup 70 70 70 The present invention also relates to a method for o ~ tention of son and fibers containing 8 to 30% acetate cellulose and 70 to 92 y of polyvinyl chloride, which consists spin a solution of polymer concentration between 15 and 30 70 by weight in a coagulating bath containing 60 to 80% by weight of dim ~ thylformamide and 20 40% water, kept low temperature preferably between 0 and THAT The filaments undergo then a first stretching which is carried out in a constituted medium water and Fe dimethylfor ~ amide, at a rate between and X, preferably at a temperature between 5 and QUE
about. The filaments are then washed gen ~ ralemen ~ water pUifi again stretched in an aqueous fluid medium at a higher temperature THAT, at a rate of 2 4 X, the total rate of stretching being included between 4 and 11 X, stabilized sign ~ és under tension in a fluid medium aqueous a temperature greater than or equal to THAT then leaflets in the free state in queux fluid medium, temperature equal or greater than.
By ordinary polyvinyl chloride is meant essential-file polyvinyl chloride having a transition temperature second order generally between 65 and QUE, consisting predominantly by the tactical isomeric form. Such a polo blackberry is obtained most commonly from the least expensive den by known techniques of mass polymerization, suspension or emulsion of temperatures gener ~ l ~ ment higher than, longer generally between y and QUE or even higher.

By the expression copolymer of polychloride Fe vinyl is also understood to mean copolymers containing minus 95 ~ (by weight) of vinyl chloride and at most 5% (in weight) of compounds comprising an ethylenic double bond, such as vinyl acetate, vinyl esters and ethers and (me acrylics, acrylonitrile, olefins such than ethylene.
The yarns and fibers according to the present invention, surprisingly have mechanical qualities and dimensional stability superior to yarns and fibers from each of the separate constituents. a particular, after retraction in boiling water, they have a Fe-Tacit of at least 20 cN / tex, preferably at least 23 cN / tex, an elongation of less than 60%, preferably less than 50 ~, these two factors being linked in an essential way to a rate residual shrinkage in boiling water less than y more generally less than y Indeed, the values of tenacity and elongation can only have real meaning related to the rate of residual withdrawal, because before the shrinkage treatment final, these two characteristics are of a higher level but then the residual withdrawal remains far too great so that such fibers can be made into con-serving interesting textile qualities.
Before performing the spinning operation, prepare the solutions in the following way: we first realize a dilute solution of cellulose acetate in dimethyl-formamide at room temperature with stirring then added preferably _ _ _____ _ _ "y.
Up to date polyvinyl chloride B0125 drilled with powder under strong ~ gltatior, kissing the temperature of 18 solution 3 minus ION
The ~ olutians, of concentration compiles between 15 and 30%
in heaps, preferably 18 to y% 9 make hot sting ~ usqu'2 THAT until di ~ sDlution conspire, then spun in a nqucux bath dimethylformamlde whose content dlmé ~ hylformamide / e ~ u by weight will Pie de yy X en dlm ~ thylfor ~ amlde ce 40 20 7. water; the bath coagulant being maintained a temperature eompr ~ between 0 and QUE.
there the flaming are resumed and ~ ublssent a first shot in a medium eon ~ consisting of water and dimethylformamlde, in proporelon 30/70 70/30 a rate between 2 and 4 X, for example per passage fur associated rollers or in a bath, a temp ~ raturle can go from 5 to 50 approximately, the value of the rate drawn depends obviously the medium, and the temperature.
In part ~ culler, the stretching is more powerful washing that the temperature would have risen too.
The filaments then wash the water, usually at counter current, temperature can speak of friend temperature gaping QUE, dash a second faith in an aqueous fluid place pure example in a sprig of boiling water or in a tube, a rate included, between 2 and 4 Y the global stretching cough removing Caux between 4 ut 11 X.
pu ensi ~ age habltu ~ lle, the filaments are stabilized SOU voltage in aqueous fluid medium temperature seen-speaker or equal THAT. Stabilization can be carried out pure example by passing through a boiling water bath or by stabilization tlQn in the presence of steam under pre ~ slon for 1 3 seconds, temperature between 105 and 13DC.
There free retraction dares insult carried out in a medium i fluid such as boiling water hanging by hand 10 Inuit preferably alder 20 minutes, or in saturated steam for example by passing through a nozzle such as rib in the . . .
y ' French patent born 83 32g / l 289 il In such a nozzle, the fila-mount its treated with steam Roture at a temperature between 105 and QUE and do sl ~ lltan ~ ment ~ etractkfi and in-its which facilitates subsequent textile transformation.
De me, when the r ~ tractlon is carried out in boiled water slot, this is preferably preceded by a mechanical crimping ion any known process.
The yarns and fibers thus obtained have characteristics mechanical ticks better than those of polychloride fibers of pure vinyl and pure cellulose acetate, by ~ iculler a better toughness, less elongation linked to a good rate of residual shrinkage, better dimensional stability during processing thermal mounts, which allows the broth dyeing of such fibers, good dye affinity for water-soluble dyes and above all an excellent absorbency according to the DON 53 814 standard, even for a small proportion of cellulose acetate which is a completely surprising element.
louves the operations since the dis601ution of polymers can be carried out continuously, so under conditions easily achievable industrially and economically lnteres6antes-Gent.
Polymers in spun solutions Delon the present application may contain usual fillers such as stabilizer, bronze, pigments, dyes, plasticizers susceptible of improvement ~
iron some of their properties such as color, refining dye, electrical resistivity, and.
Given such a procedure, filaments can be obtained at a price.
interesting able to undergo all textile operations a-r prvpriées for their finishing and to be used for the realization lion of fabrics, knitting, articles not tlss ~ s, and sank or in mixed with other yarns, which can undergo the usual treatments washing and dry cleaning under appropriate conditions without subsequent withdrawal.

The examples which live in which the parties tensioner a weight have given indicative, may born imitate pus inventlon.
In the examples, the tenacity and allon ~ e ~ ent 60nt carried out by means of a pre known in the c ~ m ~ rce HOU
INSTRON na, by measuring the maximum force that a ~ ehant ~ llon, reported its window, this force removing measured at graduation of constant elongation.
example 1 -A solution 10 in pal of gel acSLate is prepared.
lulose (acetic acid titer: 54.8 y - DP of around 180 190) in dimétbylfor ~ a ~ ide ambient temperature for agitation for 1 hour 30 minutes.
Add this cooled solution ONLY polyrhloride vinyl attic (DP of the order of 900) crazy strong agitation in quantity as it is:
- 20% by weight of ac ~ tate of cell e relative to the quantlt ~
total palym ~ rel - 20 in pDld ~ of polymers compared to the total solution.
This solution is then heated for 1 hour THAT
under quotation and we file it through a flair of 3 no holes of 0.12 mm diameter in a coagulent di ~ thylforma ~ ide / water bath:
63t32 by weight, maintained THAT
The filament is then fired in an aqueous bath.
holding 35% of dimethylfor ~ a ~ id2 maintained at 35rC a rate of 3 X.
They are then washed against ambient temperature and again in a boiling water bath At a rate of 3 X eu ensl ~ é6.
r Lea nets make sure we fix in a tube p ~ sen ~ e steam under pressure THAT for 2 seconds then donkey r ~ tractlon in boiling water for 20 minutes (trademark) The filaments obtained poss ~ derlt the characteristics following:
stranded title ~ dtex ~ 3 tenaclt ~ ~ cN / tex) extension (70) 43 residual shrinkage (boiling water) y 3 comfort index (water retention power according to DON 53 ~ 14 in J.) 74 shrinkage in saturated steam at QUE (%) 3.5 shrinkage in saturated steam QUE (%) 7.5 xample_2 -First, prepare a cellulose acetate solution in dimethylformam ~ in the manner indicated in Example 1, then add the polyvinyl chloride in the presence of 3 per 1000 of a stabilizer (relative to the polymer), the total concentration in polymer being 20% by weight and the proportion of acetate Var cellulose compared to the total weight of polymer being 20%. The dissolution is carried out at QUE for 60 minutes with stirring and we file it through a die with 3,000 holes in diameter 0.12 mm in a coagulating bath maintained at QUE consisting of 70% in weight of dimethylformamide and 30% water.
Filaments are then drawn in a maintained bath TO THAT consisting of dimethylformamide and water in a ratio weight 35/65 at a rate of 3 X, washed with counter-current water, twist in a second bath containing boiling water at a rate of 3 X, sign; the filaments are stabilized in the presence pressurized water vapor at QUE temperature laying 2 sec-elbows then retracted in a boiling water bath to QUE for r 20 minutes.
'30 The filaments obtained have the characteristics following:
stranded title (dtex) 2.60 tenacity (cN / tex) 23 elongation (% 3 43.5 residual shrinkage (boiling water) (%) 3 comfort index (water retention power according to DIX 53 814 en y 63 shrinkage in saturated steam QUE (%) 3.5

Claims (13)

The embodiments of the invention, concerning the-what an exclusive property right or lien is claimed, are defined as follows: 1. Polychlorinated filaments, threads or fibers vinyl rure and cellulose acetate, characterized by the fact that they consist of:
- 70 to 92% by weight of polyvinyl chloride or of a copo-vinyl chloride polymer containing at least 95% by weight vinyl chloride, and - 8 to 30% by weight of secondary cellulose acetate having an acetic acid content of 51.63 to 58.60%
and that they have after shrinking in boiling water a toughness of at least 20 cN / tex, an elongation at the breakage below 60%, and a residual shrinkage rate in boiling water less than 5%. 2. Filaments, threads or fibers according to the claim tion 1, characterized by the fact that they have a rate shrinkage in saturated steam at 105 ° C lower at 5%. 3. Filaments, threads or fibers according to the claim tion 1, characterized by the fact that they have a rate residual shrinkage in boiling water less than 3%. 4. Filaments, threads or fibers according to the claim tion 1, characterized by the fact that they have a tena-cited at least 23 cN / tex. 5. Filaments, threads or fibers according to the claim tion 1, characterized by the fact that they have an extension less than 50%. 6. Filaments, threads or fibers according to the claim tion 1, characterized by the fact that they have a power absorbent according to DIN 53 814 at least 50%. 7. Filaments, threads or fibers according to the claim tion 1, characterized by the fact that they have a power absorbent according to DIN 53 814 at least 70%. 8. Process for obtaining filaments, threads or fibers as defined in claim 1, characterized by the fact that we file a solution of concentration in polymers between 15 and 30%, in a coagulating bath consisting of water and dimethylformamide in weighted proportions holds between 60/80 and 20/40, maintained at a temperature rature between 0 and 20 ° C, the filaments then being drawn in water and dimethylformamide at an included rate between 2 and 4 X, washed and stretched again in a fluid medium aqueous at a temperature above 90 ° C, at a rate included between 2 and 4 X, the overall rate of stretching being between 4 and 11 X, sized and then subjected to a stabilization treatment energized in an aqueous fluid medium at a temperature equal to or greater than 100 ° C and finally retracted in the free state in an aqueous fluid medium at an equal or higher temperature at 100 ° C. 9. Method according to claim 8, characterized by the fact that the first stretching is carried out at a temperature rature between 20 and 50 ° C in a bath consisting of 30 to 70% by weight of dimethylformamide and 70 to 30% by weight of water. 10. Method according to claim 8, characterized by the fact that the second stretching is carried out in a boiling water bath. 11. Method according to claim 8, characterized by the fact that the stress stabilization treatment is carried out in a boiling water bath. 12. Method according to claim 8, characterized by the fact that the stabilization treatment is carried out in the presence of pressurized steam for 1 to 3 sec-condes at a temperature between 105 and 130 ° C. 13. Method according to claim 8, characterized by the fact that the free retraction processing is carried out killed in boiling water for at least 10 minutes.