EP0053991B1 - Filamente, Fäden, Fasern mit guten Eigenschaften aus einer Mischung von ataktischen Polyvinylchlorid und nachchloriertem Polyvinylchlorid - Google Patents

Filamente, Fäden, Fasern mit guten Eigenschaften aus einer Mischung von ataktischen Polyvinylchlorid und nachchloriertem Polyvinylchlorid Download PDF

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Publication number
EP0053991B1
EP0053991B1 EP81420155A EP81420155A EP0053991B1 EP 0053991 B1 EP0053991 B1 EP 0053991B1 EP 81420155 A EP81420155 A EP 81420155A EP 81420155 A EP81420155 A EP 81420155A EP 0053991 B1 EP0053991 B1 EP 0053991B1
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EP
European Patent Office
Prior art keywords
polyvinyl chloride
filaments
temperature
shrinkage
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81420155A
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English (en)
French (fr)
Other versions
EP0053991A1 (de
Inventor
Georges Achard
Pierre Chion
Jacques Menault
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhovyl SA
Original Assignee
Rhovyl SA
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Filing date
Publication date
Application filed by Rhovyl SA filed Critical Rhovyl SA
Publication of EP0053991A1 publication Critical patent/EP0053991A1/de
Application granted granted Critical
Publication of EP0053991B1 publication Critical patent/EP0053991B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/10—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

Definitions

  • the present invention relates to filaments, threads, fibers, monofilaments and other similar articles made of synthetic material consisting of polyvinyl chloride and superchlorinated polyvinyl chloride. It relates more particularly to threads and fibers of better mechanical qualities.
  • the fibers thus obtained can withstand heat treatment temperatures that are higher the higher the percentage of superchlorinated polyvinyl chloride in the mixture, which results in a reduction in the residual thermal shrinkage.
  • high percentages of superchlorinated polyvinyl chloride significantly increase the cost price of the son and fibers obtained, all the more so since their production process is discontinuous, in particular the heat treatment for fixing.
  • French patent n ° 85 126/1 359 178 also recommends the use of mixtures of atactic polyvinyl chloride and superchlorinated polyvinyl chloride in proportion of 5 to 50% of the mixture and specifies that the fibers obtained can, after spinning and drawing, instead of being stabilized under tension under the conditions indicated in the main patent, they are directly shrunk by heating in an appropriate medium, for example boiling water.
  • the aforementioned processing conditions only allow fibers with good properties to be obtained when the proportion of superchlorinated polyvinyl chloride is relatively large.
  • the toughness and elongation of the yarns obtained are good thanks to the relatively large proportion of superchlorinated polyvinyl chloride: 20% by weight.
  • the difficulty with this type of atactic polyvinyl chloride and superchlorinated polyvinyl chloride mixture therefore consists, in fact, of finding a compromise making it possible to obtain fibers having the highest possible mechanical qualities for the lowest possible cost price.
  • the present invention relates to yarns and fibers based on a mixture of atactic polyvinyl chloride and superchlorinated polyvinyl chloride with good mechanical characteristics, even for mixtures containing little superchlorinated polyvinyl chloride, obtained by means of a continuous industrial process, that is to say under the most economical conditions possible.
  • the modulus of elasticity is between 3 and 5 kN / mm 2 , the shrinkage constraint, after shrinking in an aqueous fluid medium at a temperature between 98 and 130 ° C between 2 and 3.5 10-2 g / dtex, and the residual shrinkage in boiling water less than or equal to 1%.
  • the present invention also relates to a process for obtaining filaments, threads, fibers based on a mixture of atactic polyvinyl chloride and superchlorinated polyvinyl chloride, characterized in that after spinning said mixture in solution in a manner known per se , filaments are drawn in boiling water at a rate between 3 and 6X, stabilized continuously under tension at a temperature between 105 ° and 130 ° C in the presence of steam under pressure for 1 to 3 seconds then shrinkage at a temperature between 98 and 130 ° C in an aqueous fluid medium.
  • the term “atactic polyvinyl chloride” is understood to mean essentially the homopolymer of vinyl chloride having a second order transition temperature generally between 65 ° and 85 ° C.
  • Polyvinyl chloride is predominantly constituted by the atactic isomer form, that is to say that it is a polymer whose chlorine and hydrogen atoms are predominantly located randomly on both sides of the chain constituting the skeleton of the molecule. Therefore, such a polymer is normally of a non-crystallizable nature.
  • Such a polymer is most commonly obtained in the least costly manner by known techniques of bulk polymerization, suspension or emulsion at temperatures generally above 0 ° C, more generally between 20 and 60 ° C or even more.
  • the superchlorinated polyvinyl chloride usable according to the present invention can be obtained for example, by chlorination of a suspension of polyvinyl chloride in the presence of actinic light, or by chlorination at high temperature, or in the presence of active chemical radiation; it generally has a second order transition temperature of at least 100 ° C.
  • the process of the invention can also be applied to mixtures containing more than 20% of superchlorinated polyvinyl chloride and in this case also leads to better mechanical qualities of the threads, but the articles thus produced have a higher cost price.
  • the yarns and fibers according to the present invention have a high elastic modulus, at least 3 kN / mm 2 generally between 3 and 5 kN / mm 2 .
  • a modulus of elasticity is high for fibers based on a mixture of polyvinyl chloride / superchlorinated polyvinyl chloride, the modulus of which is generally of the order of 2 to 2.5 kN / mm 2 for the same proportion of polychloride of superchlorinated vinyl.
  • This high value of the modulus of elasticity of the yarns and fibers according to the invention is all the more advantageous since it is accompanied by a very low rate of residual shrinkage in boiling water: less than 2%, more generally less than 1% or even 0.5%.
  • the shrinkage constraint of the filaments is measured by means of a retractometer: the filament samples of length 4 cm, assembled in the form of test tubes of 400 dtex on average (each test being carried out on two test tubes) are submitted, after each different stages of stretching, stabilization and finally retraction, at a temperature rise of 1 ° C per minute, from 30 ° C to 170 ° C. Measuring the shrinkage force expressed as 10- 2 g / dtex on each test specimen as a function of temperature. This withdrawal constraint or withdrawal force in each case passes through a maximum at a certain temperature. It is this maximum withdrawal force which represents the molecular orientation characteristic of the products, which is designated by withdrawal constraint.
  • the yarns and fibers obtained according to the present application retain, after the last phase of the process, that is to say the retraction in the aqueous fluid, a shrinkage stress of at least 1.6 10-2 g / dtex while yarns based on polyvinyl chloride / superchlorinated polyvinyl chloride mixtures as obtained according to the example of patent 85126/1359178 have, after shrinking in boiling water, a shrinkage stress of 1 10-2 g / dtex, this for an identical proportion of superchlorinated polyvinyl chloride relative to the mixture (cf. the comparative example below).
  • the yarns and fibers according to the present invention can be obtained according to any known process such as for example spinning in solution by a dry or wet process, preferably dry.
  • Solutions can be used in known solvents or solvent mixtures such as perchlorethylene / acetone mixtures, tetrahydrofuran, cyclohexanone, benzene / acetone mixtures or carbon sulfide / acetone in appropriate proportions, this list not being limiting.
  • the filaments are coagulated in a non-solvent bath of the polymer mixture but miscible with the solvent whereas, according to the dry spinning process, the solvent is evaporated by means of hot air and generally recovered.
  • the polymer concentration of the solutions is generally of the order of 20-30% by weight according to the dry spinning process and only 10-20% by weight according to the wet spinning process, the solutions preferably being in each case filtered before spinning to remove frost or dirt particles that could clog the holes in the die.
  • the filaments are drawn to give them a molecular orientation and to improve their mechanical characteristics, at a rate of between 3 and 6 ⁇ .
  • the drawing of the filaments according to the present invention comprises a preheating for example in water at temperatures between 60 and 100 ° C, more generally between 75 and 85 ° C.
  • One practical way is to use a heated water bath.
  • the actual stretching can be carried out in 1 or 2 stages, but it is preferable to gradually raise the temperature of the filaments by preheating, pre-stretching for example in a bath whose water can be maintained between 70 ° and 95 ° C then continuous stretching at a temperature slightly higher than that of the pre-stretching, preferably between 85 ° and 100 ° C.
  • the overall stretching rate being of the order of 3 to 6 ⁇ , preferably of 3.5 to 5.
  • To be able to obtain an overall drawing rate of 6 it is easier to limit the drawing of the filaments just after the die, by adjusting the speed of the take-up rollers.
  • the filaments thus drawn are then subjected to tension stabilization to avoid any shrinkage, in the presence of pressurized steam at a temperature between 105 and 130 ° C, preferably between 110-120 ° C for 1 to 3 seconds.
  • a free shrinkage which can be carried out in boiling water for a variable duration, for example at least 10 minutes, in general from 10 to 20 minutes or even more or in steam.
  • saturated water for example by passing through a nozzle such as that described in French patent 83 329/1 289491. In such a nozzle the filaments are treated with saturated steam at a temperature between 110 ° and 130 ° and are simultaneously shrunk and crimped which allows better subsequent textile workability.
  • the process according to the present invention can be carried out completely continuously from the drawing or even from the dissolution of the polymers until the final yarns or fibers are obtained. Therefore, it is easy to carry out industrially economically.
  • the polymers or solutions spun according to the present application can contain usual fillers such as stabilizers with respect to light, heat, brighteners, pigments, dyes capable of improving some of their properties such as their color, dye affinity, thermal and light stability, electrical resistivity.
  • Such a process leads to filaments with better mechanical characteristics than those of yarns based on polyvinyl chloride / chlorinated polyvinyl chloride mixtures obtained according to French patents 1,359,178 and 85,126 / 1,359,178 with a content of equal superchlorinated polyvinyl chloride. . They are also better than those of filaments based on atactic polyvinyl chloride alone treated according to the method of the present invention which is the subject of a patent application filed the same day.
  • the filaments and fibers according to the present invention can undergo all the appropriate textile transformations and can be used for the production of fabrics, knits, non-woven articles, alone or in mixtures with other fibers and can in particular undergo all the usual washing treatments. and dry cleaning under appropriate conditions.
  • Said yarns and fibers according to the invention are also particularly appreciated in the textile field because of certain properties inherent in the composition of the mixtures: non-flammability, resistance to light, chemical inertness and power of thermal, electrical and acoustic insulation.
  • a polymer solution with a concentration of 28% by weight is prepared in a solvent mixture of carbon sulphide / acetone at 50/50 by volume.
  • the polymer consists of a mixture of 82.5% by weight of polyvinyl chloride predominantly atactic (AFNOR index: 120 - according to AFNOR standard T 51-013 - chlorine level 56.5%) and 17.5% of superchlorinated polyvinyl chloride having a chlorine level of 69% and an AFNOR index of 110.
  • the solution thus obtained is filtered and, while being maintained at approximately 70 ° C., is spun through a die having 908 orifices of 0.06 mm in diameter in a dry spinning cell allowing the continuous recovery of the solvent mixture such as described in French patent 913 927.
  • the filaments are then preheated in a water bath maintained at 80 ° C and then drawn a first time in a water bath maintained at 85 ° C at a rate of 2.9 X, then drawn a second time in a second water bath maintained at 95 ° C at a rate of 1.2 X, (total rate 3.5 X).
  • the filaments are then stabilized continuously under tension in a tube containing saturated steam at 105 ° C, the inlet and outlet speeds of the filaments being strictly identical, and the residence time in the tube being 2 seconds.
  • the filaments then undergo mechanical crimping and free shrinking in boiling water for 20 minutes.
  • the filaments thus obtained have the characteristics given in the table below.
  • Example 1 is reproduced by only modifying the stabilization temperature in the tube in the presence of saturated steam which is 110 ° C.
  • the filaments obtained have the characteristics given in the table below.
  • Example 1 is reproduced exactly, but by stabilizing the filaments in the presence of water vapor at a temperature of 120 ° C.
  • Example 2 For comparison, a solution of a mixture of polymers identical to that described in Example 1 is spun under the conditions indicated above.
  • the filaments are drawn under the same conditions and at the same rate; before and after direct shrinking in boiling water for 20 minutes, they have the following characteristics:
  • Example 1 A solution identical to that described in Example 1 is prepared and it is spun in the same way through an identical die.
  • the filaments are then preheated in a water bath maintained at 80 ° C., then drawn a first time in a water bath at 85 ° C. at a rate of 2.5 ⁇ and then drawn again at a rate of 1, 46 X in a bath at 95 ° C so as to obtain a total stretch of 3.65 X.
  • the filaments then undergo, continuously, a stabilization treatment in the presence of vapor under pressure at 105 ° C., for two seconds, under tension, the speeds of entry and exit of the filaments being identical.
  • the filaments then pass continuously through a nozzle as described in French patent 83329/1 289491 where they are continuously subjected to a shrinkage treatment in water vapor at an average temperature of 120 ° C and crimped.
  • the toughness measurements are carried out by means of an apparatus known in the trade under the name of "INSTRON", by measurement of the maximum force which a sample supports with respect to its title, this force being measured at constant elongation gradient.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Claims (8)

1. Filamente, Fäden, Fasern auf Basis eines Gemisches ataktisches Polyvinylchlorid/überchloriertes Polyvinylchlorid, wobei letzteres in einer Menge zwischen 16 und 20 Gewichtsprozent in bezug auf das Gemisch vorliegt, dadurch gekennzeichnet, daß sie besitzen :
- einen Restschrumpfungswert in siedendem Wasser unterhalb 2 %,
- einen Elastizitätsmodul gleich oder größer 3 kN/mm2,
- eine Schrumpfspannung nach Schrumpfung in wässerigem, fluidem Milieu bei einer Temperatur zwischen 98° und 130°C, gleich oder größer als 1,6 - 10-2 g/dtex.
2. Filamente, Fäden, Fasern gemäß Anspruch 1, dadurch gekennzeichnet, daß der Restschrumpfungswert in siedendem Wasser gleich oder unterhalb 1 % ist, der Elastizitätsmodul zwischen 3 und 5 kN/mm2 liegt und die Schrumpfspannung nach Schrumpfung in fluidem wässerigem Milieu bei einer Temperatur zwischen 98° und 130 °C zwischen 2 und 3,5 - 10-2 g/dtex beträgt.
3. Verfahren zur Herstellung von Filamenten, Fäden, Fasern auf Basis eines Gemisches ataktisches Polyvinylchlorid/überchloriertes Polyvinylchlorid, dadurch gekennzeichnet, daß nach dem Verspinnen dieses Gemisches in Lösung in bekannter Weise die Fäden in siedendem Wasser auf einen Wert zwischen 3- und 6-fach verstreckt werden, daß sie kontinuierlich unter Spannung bei einer Temperatur zwischen 105° und 130 °C in Gegenwart von Dampf unter Druck während 1 bis 3 Sekunden stabilisert werden und daß sie dann in fluidem wässerigem Milieu bei einer Temperatur zwischen 98° und 130 °C geschrumpft werden.
4. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß die Streckungsphase umfasst ;
- ein Vorerhitzen der Fäden,
- ein Vorverstrecken der Fäden bei einer Temperatur zwischen 70° und 95 °C,
- ein zweites Verstreckungsstadium bei einer Temperatur zwischen 85° und 100 °C.
5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß die Stabilisierungsphase bei einer Temperatur zwischen 110° und 120 °C bewirkt wird.
6. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß die Schrumpfung in siedendem Wasser während wenigstens 10 Minuten durchgeführt wird.
7. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß die Schrumpfung in Gegenwart von gesättigtem Dampf bei einer Temperatur zwischen 110° und 130 °C durchgeführt wird.
8. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß die Fäden nach der Stabilisierungsphase eine mechanische Kräuselung erleiden.
EP81420155A 1980-12-08 1981-10-29 Filamente, Fäden, Fasern mit guten Eigenschaften aus einer Mischung von ataktischen Polyvinylchlorid und nachchloriertem Polyvinylchlorid Expired EP0053991B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8026047A FR2495646A1 (fr) 1980-12-08 1980-12-08 Fils et fibres de bonnes proprietes a base de melange de polychlorure de vinyle et de polychlorure de vinyle surchlore et procede pour leur obtention
FR8026047 1980-12-08

Publications (2)

Publication Number Publication Date
EP0053991A1 EP0053991A1 (de) 1982-06-16
EP0053991B1 true EP0053991B1 (de) 1984-04-11

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EP81420155A Expired EP0053991B1 (de) 1980-12-08 1981-10-29 Filamente, Fäden, Fasern mit guten Eigenschaften aus einer Mischung von ataktischen Polyvinylchlorid und nachchloriertem Polyvinylchlorid

Country Status (9)

Country Link
US (1) US4780368A (de)
EP (1) EP0053991B1 (de)
JP (1) JPS57167412A (de)
AR (1) AR231732A1 (de)
BR (1) BR8108319A (de)
CA (1) CA1173612A (de)
DE (1) DE3163105D1 (de)
ES (1) ES8207238A1 (de)
FR (1) FR2495646A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2524475A1 (fr) * 1982-04-01 1983-10-07 Rhovyl Solutions a base de polychlorure de vinyle, leur procede d'obtantion et fils et fibres ainsi obtenus
FR2579637B1 (fr) * 1985-03-26 1988-03-18 Rhovyl Procede de teinture de fils et fibres a base de polychlorure de vinyle
FR2579636B1 (fr) * 1985-03-26 1988-03-18 Rhovyl Procede de teinture de fils et fibres a base de polychlorure de vinyle
FR2680525B1 (fr) * 1991-08-23 1996-04-12 Rhovyl Fibres a base de melanges pvc/pvc chlore possedant des proprietes mecaniques ameliorees et files de fibres de tenacite amelioree obtenus a partir de ces fibres.
US6933024B2 (en) * 2002-07-18 2005-08-23 Hewlett-Packard Development Company, L.P. Water soluble polymers as inkjet recording materials
JP5700048B2 (ja) * 2010-10-06 2015-04-15 株式会社カネカ ポリ塩化ビニル系樹脂繊維の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1359178A (fr) * 1963-02-12 1964-04-24 Rhovyl Sa Fibres synthétiques à base de chlorure de polyvinyle
AT292177B (de) * 1963-07-31 1971-08-10 Chatillon Italiana Fibre Verfahren zur Herstellung von wärmeschrumpffähigen Fasern aus Polyvinylchlorid
BE791829A (fr) * 1971-11-26 1973-05-23 Bayer Ag Filaments et fibres en chlorure de polyvinyle syndiotactique

Also Published As

Publication number Publication date
FR2495646A1 (fr) 1982-06-11
FR2495646B1 (de) 1984-03-09
US4780368A (en) 1988-10-25
BR8108319A (pt) 1982-10-05
ES507734A0 (es) 1982-09-01
CA1173612A (fr) 1984-09-04
EP0053991A1 (de) 1982-06-16
DE3163105D1 (en) 1984-05-17
AR231732A1 (es) 1985-02-28
JPS57167412A (en) 1982-10-15
ES8207238A1 (es) 1982-09-01
JPH0152487B2 (de) 1989-11-09

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