EP0053991B1 - Good quality filaments, threads, fibres from a mixture of atactic polyvinyl chloride and overchlorinated polyvinyl chloride, and process for their manufacture - Google Patents
Good quality filaments, threads, fibres from a mixture of atactic polyvinyl chloride and overchlorinated polyvinyl chloride, and process for their manufacture Download PDFInfo
- 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
- Authority
- 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
Links
- 229920000915 polyvinyl chloride Polymers 0.000 title claims description 46
- 239000004800 polyvinyl chloride Substances 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 8
- 230000006641 stabilisation Effects 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002788 crimping Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000011105 stabilization Methods 0.000 description 6
- 239000004753 textile Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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.
Landscapes
- 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)
Description
La présente invention concerne des filaments, fils, fibres, monofilaments et autres articles similaires en matière synthétique constitués de polychlorure de vinyle et de polychlorure de vinyle surchloré. Elle concerne plus particulièrement des fils et fibres de meilleures qualités mécaniques.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.
Il est déjà connu selon le brevet français 1 359178 de préparer des fils et fibres constitués de mélanges de polychlorure de vinyle ordinaire et polychlorure de vinyle ordinaire et polychlorure de vinyle surchloré, ce dernier étant présent en proportion comprise entre 5 % et 80 %, de préférence au moins 10%.It is already known according to French patent 1 359178 to prepare yarns and fibers made up of mixtures of ordinary polyvinyl chloride and ordinary polyvinyl chloride and superchlorinated polyvinyl chloride, the latter being present in a proportion of between 5% and 80%, preferably at least 10%.
Les fibres ainsi obtenues peuvent supporter des températures de traitement thermique d'autant plus élevées que le pourcentage en polychlorure de vinyle surchloré dans le mélange est élevé, ce qui a pour conséquence une diminution du retrait thermique résiduel. Par contre, des pourcentages élevés en polychlorure de vinyle surchloré augmentent de manière importante le prix de revient des fils et fibres obtenus, ceci d'autant plus que leur procédé d'obtention est discontinu, en particulier le traitement thermique de fixation.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. On the other hand, 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.
Le brevet français n° 85 126/1 359 178 préconise également l'utilisation de mélanges de polychlorure de vinyle atactique et chlorure de polyvinyle surchloré en proportion de 5 à 50 % du mélange et précise que les fibres obtenues peuvent, après filage et étirage, au lieu d'être stabilisées sous tension dans les conditions indiquées dans le brevet principal, être directement rétractées par chauffage dans un milieu approprié, par exemple l'eau bouillante. Mais, en pratique, les conditions de traitement précitées ne permettent l'obtention de fibres de bonnes propriétés que lorsque la proportion de polychlorure de vinyle surchloré est relativement importante. Dans l'exemple unique de ce brevet, les ténacités et allongements des fils obtenus sont bons grâce à la proportion relativement importante en polychlorure de vinyle surchloré : 20 % en poids. Par contre pour des teneurs en polychlorure de vinyle surchloré inférieures et des taux d'étirage moindres, de telles qualités sont impossibles à obtenir par rérétraction directe dans l'eau bouillante. A partir de 20 % en poids de polychlorure de vinyle surchloré et au-delà, si les qualités mécaniques des fibres sont bien meilleures, leur prix de revient augmente aussi en conséquence.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. However, in practice, the aforementioned processing conditions only allow fibers with good properties to be obtained when the proportion of superchlorinated polyvinyl chloride is relatively large. In the unique example of this patent, the toughness and elongation of the yarns obtained are good thanks to the relatively large proportion of superchlorinated polyvinyl chloride: 20% by weight. On the other hand, for lower contents of superchlorinated polyvinyl chloride and lower drawing rates, such qualities are impossible to obtain by direct retraction in boiling water. From 20% by weight of superchlorinated polyvinyl chloride and beyond, if the mechanical qualities of the fibers are much better, their cost price also increases accordingly.
La difficulté avec ce type de mélange polychlorure de vinyle atactique et polychlorure de vinyle surchloré consiste donc, en fait, à trouver un compromis permettant d'obtenir des fibres possédant les qualités mécaniques les plus élevées possibles pour le prix de revient le plus faible possible.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.
La présente invention concerne des fils et fibres à base d'un mélange polychlorure de vinyle atactique et polychlorure de vinyle surchloré de bonnes caractéristiques mécaniques, même pour des mélanges contenant peu de polychlorure de vinyle surchloré, obtenues au moyen d'un procédé industriel continu, c'est-à-dire dans des conditions les plus économiques possibles.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.
De manière plus précise, elle concerne des filaments, fibres, fils à base d'un mélange de polychlorure de vinyle atactique et polychlorure de vinyle surchloré, ce dernier étant présent en proportion comprise entre 16 et 20 % en poids par rapport au mélange, caractérisés par le fait qu'ils possèdent un taux de retrait résiduel dans l'eau bouillante inférieur à 2 %, un module d'élasticité égal ou supérieur à 3 kN/mm2, et une contrainte de retrait, après rétraction en milieu fluide aqueux à température comprise entre 98° et 130°C, égale ou supérieure à 1,6 - 10-2 g/dtex.More specifically, it relates to filaments, fibers, yarns based on a mixture of atactic polyvinyl chloride and superchlorinated polyvinyl chloride, the latter being present in a proportion of between 16 and 20% by weight relative to the mixture, characterized by the fact that they have a residual shrinkage rate in boiling water of less than 2%, a modulus of elasticity equal to or greater than 3 kN / mm 2 , and a shrinkage stress, after shrinking in an aqueous fluid medium at temperature between 98 ° and 130 ° C, equal to or greater than 1.6 - 10-2 g / dtex.
De préférence, le module d'élasticité est compris entre 3 et 5 kN/mm2, la contraite de retrait, après rétraction en milieu fluide aqueux à température comprise entre 98 et 130 °C entre 2 et 3,5 10-2 g/dtex, et le retrait résiduel dans l'eau bouillante inférieur ou égal à 1 %.Preferably, 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%.
La présente invention concerne également un procédé pour l'obtention de filaments, fils, fibres à base d'un mélange de polychlorure de vinyle atactique et polychlorure de vinyle surchloré, caractérisé par le fait que après filage en solution dudit mélange de manière connue en soi, des filaments sont étirés dans l'eau bouillante à un taux compris entre 3 et 6X, stabilisés en continu sous tension à une température comprise entre 105° et 130 °C en présence de vapeur d'eau sous pression pendant 1 à 3 secondes puis rétraction à température comprise entre 98 et 130 °C en milieu fluide aqueux.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.
On entend par polychlorure de vinyle atactique essentiellement l'homopolymère de chlorure de vinyle ayant une température de transition de second ordre comprise généralement entre 65° et 85 °C. Le polychlorure de vinyle est constitué de façon prédominante par la forme isomère atactique, c'est-à-dire qu'il s'agit d'un polymère dont les atomes de chlore et d'hydrogène sont en majorité situés au hasard des deux côtés de la chaîne constituant le squelette de la molécule. De ce fait, un tel polymère est normalement d'une nature non cristallisable. Un tel polymère est obtenu le plus couramment de la manière la moins onéreuse par les techniques connues de polymérisation en masse, suspension ou émulsion à des températures généralement supérieures à 0°C, plus généralement comprises entre 20 et 60 °C ou même plus.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.
Le polychlorure de vinyle surchloré utilisable selon la présente invention peut être obtenu par exemple, par chloration d'une suspension de polychlorure de vinyle en présence de lumière actinique, ou par chloration à haute température, ou en présence de rayonnements chimiques actifs ; il possède généralement une température de transition du second ordre d'au moins 100 °C.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.
Le procédé de l'invention peut aussi être appliqué à des mélanges contenant plus de 20 % en polychlorure de vinyle surchloré et dans ce cas conduit également à de meilleures qualités mécaniques des fils mais les articles ainsi produits possèdent un prix de revient supérieur.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.
Il est possible de descendre en dessous d'une proportion de 16 % en polychlorure de vinyle surchloré (par exemple jusqu'à 12 % ou même 10 %) mais les conditions du procédé doivent alors être optimales pour que les fils obtenus possèdent des qualités mécaniques acceptables. Par exemple, il faut alors que les fils soient étirés très près du maximum de leur étirabilité et que la température de stabilisation soit portée également à son maximum en évitant toutefois les risques de casse ou de collage, ce qui diminuerait la souplesse du procédé selon l'invention.It is possible to fall below a proportion of 16% in superchlorinated polyvinyl chloride (for example up to 12% or even 10%) but the conditions of the process must then be optimal so that the wires obtained have mechanical qualities acceptable. For example, it is then necessary that the strands are drawn very close to the maximum of their stretchability and that the stabilization temperature is also brought to its maximum, however avoiding the risks of breakage or sticking, which would reduce the flexibility of the process according to 'invention.
Les fils et fibres selon la présente invention possèdent un module d'élasticité élevé, au moins 3 kN/mm2 généralement compris entre 3 et 5 kN/mm2. Un tel module d'élasticité est élevé pour des fibres à base de mélange polychlorure de vinyle/polychlorure de vinyle surchloré, dont le module est généralement de l'ordre de 2 à 2,5 kN/mm2 pour une même proportion de polychlorure de vinyle surchloré. Ceci est un fait important car le module est représentatif des caractéristiques mécaniques des fibres obtenues (résistance et allongement) et permet une bonne travaillabilité des fils et fibres sans que ceux-ci prennent du retrait au cours du travail textile ultérieur. Cette valeur élevée du module d'élasticité des fils et fibres selon l'invention est d'autant plus intéressante qu'elle s'accompagne d'un très faible taux de retrait résiduel dans l'eau bouillante : inférieur à 2 %, plus généralement inférieur à 1 % ou même à 0,5 %.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 . Such 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 is an important fact because the module is representative of the mechanical characteristics of the fibers obtained (strength and elongation) and allows good workability of the threads and fibers without the latter taking shrinkage during subsequent textile work. 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%.
En effet, il est habituellement plus aisé d'obtenir sur des fils à base de polychlorure de vinyle de bons modules d'élasticité si l'on se contente de retraits résiduels plus élevés, par exemple de l'ordre de 5 % ou plus. Mais de telles caractéristiques conduisent à des difficultés difficilement surmontables au stade du travail textile ultérieur.Indeed, it is usually easier to obtain on polyvinyl chloride yarns good elastic moduli if one is satisfied with higher residual shrinkages, for example of the order of 5% or more. However, such characteristics lead to difficulties which are difficult to overcome at the stage of subsequent textile work.
De plus, on parvient sur les fils et fibres selon la présente invention à une meilleure maîtrise de leur degré d'orientation au stade final, c'est-à-dire après rétraction dans le fluide aqueux. Dans la présente demande le degré d'orientation est exprimé par les contraintes de retrait des fils et fibres obtenus.In addition, on the yarns and fibers according to the present invention, better control of their degree of orientation is achieved at the final stage, that is to say after retraction in the aqueous fluid. In the present application the degree of orientation is expressed by the constraints of withdrawal of the son and fibers obtained.
La contrainte de retrait des filaments est mesurée au moyen d'un rétractomètre : les échantillons de filaments de longueur 4 cm, assemblés sous forme d'éprouvettes de titre 400 dtex en moyenne (chaque essai étant effectué sur deux éprouvettes) sont soumis, après chacune des différentes étapes d'étirage, de stabilisation et enfin de rétraction, à une élévation de température de 1 °C par minute, de 30 °C à 170 °C. On mesure la force de rétraction exprimée en 10-2 g/dtex sur chaque éprouvette en fonction de la température. Cette contrainte de retrait ou force de retrait passe dans chaque cas par un maximum à une certaine température. C'est cette force de retrait maximale qui représente la caractéristique d'orientation moléculaire des produits, que l'on désigne par contrainte de retrait.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.
Les fils et fibres obtenus selon la présente demande conservent après la dernière phase du procédé, c'est-à-dire la rétraction dans le fluide aqueux, une contrainte de retrait d'au moins 1,6 10-2 g/dtex alors que les fils à base de mélanges polychlorure de vinyle/polychlorure de vinyle surchloré tels que obtenus selon l'exemple du brevet 85126/1359178 possèdent, après rétraction dans l'eau bouillante, une contrainte de retrait de 1 10-2 g/dtex, ceci pour une proportion identique en polychlorure de vinyle surchloré par rapport au mélange (cf. l'exemple comparatif ci-dessous).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).
Les fils et fibres selon la présente invention peuvent être obtenus selon tout procédé connu comme par exemple le filage en solution par un procédé à sec ou à l'humide, de préférence à sec.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.
On peut utiliser des solutions dans des solvants ou mélanges solvants connus tels que les mélanges perchloréthylène/acétone, le tétrahydrofuranne, la cyclohexanone, les mélanges benzène/acétone ou sulfure de carbone/acétone dans des proportions appropriées, cette liste n'étant pas limitative.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.
Selon le procédé de filage humide, les filaments sont coagulés dans un bain non solvant du mélange polymère mais miscible avec le solvant alors que selon le procédé de filage à sec, le solvant est évaporé au moyen d'air chaud et généralement récupéré. La concentration en polymère des solutions est généralement de l'ordre de 20-30 % en poids selon le procédé de filage à sec et seulement de 10-20 % en poids selon le procédé de filage humide, les solutions étant dans chaque cas de préférence filtrées avant le filage pour éliminer les particules de gel ou salissures susceptibles d'obstruer les orifices de la filière.According to the wet spinning process, 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.
Après le filage qui est effectué de préférence à sec, les filaments sont étirés pour leur conférer une orientation moléculaire et améliorer leurs caractéristiques mécaniques, à un taux compris entre 3 et 6 X. De préférence l'étirage des filaments selon la présente invention comprend un préchauffage par exemple dans l'eau à des températures comprises entre 60 et 100 °C, plus généralement entre 75 et 85 °C. Un moyen pratique consiste à utiliser un bain d'eau chauffé. L'étirage proprement dit peut être effectué en 1 ou 2 stades, mais on préfère élever progressivement la température des filaments par préchauffage, préétirage par exemple dans un bain dont l'eau peut être maintenue entre 70° et 95 °C puis étirage en continu à une température un peu plus élevée que celle du préétirage, de préférence entre 85° et 100 °C le taux d'étirage global étant de l'ordre de 3 à 6 X, de préférence de 3,5 à 5. Pour pouvoir obtenir un taux d'étirage global de 6 il est plus facile de limiter l'étirage des filaments juste après la filière, par réglage de la vitesse des rouleaux de reprise.After spinning, which is preferably carried out dry, the filaments are drawn to give them a molecular orientation and to improve their mechanical characteristics, at a rate of between 3 and 6 ×. Preferably 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.
Les filaments ainsi étirés subissent ensuite une stabilisation sous tension pour éviter tout retraif, en présence de vapeur d'eau sous pression à une température comprise entre 105 et 130 °C de préférence entre 110-120 °C pendant 1 à 3 secondes.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.
Après stabilisation ils sont soumis de préférence en continu à une rétraction libre qui peut être effectuée dans l'eau bouillante pendant une durée variable, par exemple au moins 10 minutes, en général de 10 à 20 minutes ou même plus ou dans la vapeur d'eau saturée par exemple par passage dans une buse telle que celle décrite dans le brevet français 83 329/1 289491. Dans une telle buse les filaments sont traités par de la vapeur d'eau saturée à une température comprise entre 110° et 130° et sont simultanément rétractés et frisés ce qui permet une meilleure travaillabilité textile ultérieure.After stabilization they are preferably subjected continuously to 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.
Dans le cas où la rétraction est effectuée dans l'eau bouillante celle-ci est de préférence précédée d'un frisage mécanique selon tout procédé connu, également dans le but de faciliter la travaillabilité ultérieure.In the case where the retraction is carried out in boiling water, this is preferably preceded by mechanical crimping according to any known process, also with the aim of facilitating subsequent workability.
Le procédé selon la présente invention peut être réalisé totalement en continu depuis l'étirage ou même depuis la dissolution des polymères jusqu'à l'obtention des fils ou fibres définitifs. De ce fait, il est facile à réaliser industriellement de manière économique.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.
Les polymères ou solutions filées selon la présente demande peuvent contenir des charges habituelles telles que des stabilisants vis-à-vis de la lumière, de la chaleur, azurants, pigments, colorants susceptibles d'améliorer certaines de leurs propriétés telles que leur couleur, l'affinité tinctoriale, la stabilité thermique et à la lumière, la résistivité électrique.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.
Un tel procédé conduit à des filaments de caractéristiques mécaniques meilleures que celles de fils à base de mélanges polychlorure de vinyle/polychlorure de vinyle chloré obtenus selon les brevets français 1 359 178 et 85 126/1 359 178 à teneur en polychlorure de vinyle surchloré égale. Elles sont également meilleures que celles de filaments à base de polychlorure de vinyle atactique seul traité selon le procédé de la présente invention qui fait l'objet d'une demande de brevet déposée le même jour.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.
Les filaments et fibres selon la présente invention peuvent subir toutes les transformations textiles appropriées et sont utilisables pour la réalisation de tissus, tricots, articles non tissés, seuls ou en mélanges avec d'autres fibres et peuvent en particulier subir tous les traitements habituels de lavage et nettoyage à sec dans des conditions appropriées.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.
Lesdits fils et fibres selon l'invention sont en outre particulièrement appréciés dans le domaine textile en raison de certaines propriétés inhérentes à la composition des mélanges : ininflammabilité, résistance à la lumière, inertie chimique et pouvoir d'isolation thermique, électrique et acoustique.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.
Les exemples qui suivent dans lesquels les parties s'entendent en poids sont donnés à titre indicatif mais non limitatif.The examples which follow in which the parts are by weight are given as an indication but are not limiting.
On prépare une solution de polymère de concentration 28 % en poids, dans un mélange solvant sulfure de carbone/acétone à 50/50 en volume.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.
Le polymère est constitué d'un mélange de 82,5 % en poids de polychlorure de vinyle à prédominance atactique (indice AFNOR : 120 - selon la norme AFNOR T 51-013 - taux de chlore 56,5 %) et 17,5 % de polychlorure de vinyle surchloré possédant un taux de chlore de 69 % et un indice AFNOR de 110.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.
La solution ainsi obtenue est filtrée et, tout en étant maintenue à 70 °C environ, est filée à travers une filière comportant 908 orifices de 0,06 mm de diamètre dans une cellule de filage à sec permettant la récupération continue du mélange solvant telle que décrite dans le brevet français 913 927. Les filaments sont ensuite préchauffés dans un bain d'eau maintenu à 80 °C puis étirés une première fois dans un bain d'eau maintenu à 85°C à un taux de 2,9 X, puis étirés une seconde fois dans un second bain d'eau maintenu à 95°C à un taux de 1,2 X, (taux total 3,5 X). Les filaments sont ensuite stabilisés en continu sous tension dans un tube contenant de la vapeur saturée à 105 °C, les vitesses d'entrée et de sortie des filaments étant rigoureusement identiques, et le temps de séjour dans le tube étant de 2 secondes.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.
Les filaments subissent ensuite un frisage mécanique et une rétraction libre dans l'eau bouillante pendant 20 minutes.The filaments then undergo mechanical crimping and free shrinking in boiling water for 20 minutes.
Les filaments ainsi obtenus possèdent les caractéristiques données dans le tableau ci-dessous.The filaments thus obtained have the characteristics given in the table below.
On reproduit l'exemple 1 en modifiant seulement la température de stabilisation dans le tube en présence de vapeur d'eau saturée qui est de 110 °C. Les filaments obtenus présentent les caractéristiques données dans le tableau ci-dessous.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.
On reproduit exactement l'exemple 1 mais en stabilisant les filaments en présence de vapeur d'eau à une température de 120 °C.Example 1 is reproduced exactly, but by stabilizing the filaments in the presence of water vapor at a temperature of 120 ° C.
Les caractéristiques des filaments sont groupées dans le tableau ci-dessous :The characteristics of the filaments are grouped in the table below:
A titre de comparaison, une solution d'un mélange de polymères identique à celui décrit dans l'exemple 1 est filé dans les conditions indiquées ci-dessus. Les filaments sont étirés dans les mêmes conditions et à un même taux ; ils possèdent avant et après rétraction directe dans l'eau bouillante pendant 20 minutes les caractéristiques suivantes :
On prépare une solution identique à celle décrite dans l'exemple 1 et on la file de la même manière à travers une filière identique.A solution identical to that described in Example 1 is prepared and it is spun in the same way through an identical die.
Les filaments sont ensuite préchauffés dans un bain d'eau maintenu à 80 °C, puis étirés une première fois dans un bain d'eau à 85 °C à un taux de 2,5 X puis étirés de nouveau à un taux de 1,46 X dans un bain à 95 °C de manière à obtenir un étirage total de 3,65 X.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.
Les filaments subissent ensuite, en continu, un traitement de stabilisation en présence de vapeur sous pression à 105 °C, pendant deux secondes, sous tension, les vitesses d'entrée et sortie des filaments étant identiques.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.
Les filaments passent ensuite en continu dans une buse telle que décrite dans le brevet français 83329/1 289491 où ils sont soumis en continu à un traitement de rétraction dans la vapeur d'eau à une température moyenne de 120 °C et frisés.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.
Les caractéristiques des filaments obtenus sont les suivantes :
Dans les exemples ci-dessus, les mesures de ténacités sont effectuées au moyen d'un appareil connu dans le commerce sous le nom d'« INSTRON », par mesure de la force maximale que supporte un échantillon rapportée à son titre, cette force étant mesurée à gradient d'allongement constant.In the above examples, 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.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8026047 | 1980-12-08 | ||
| FR8026047A FR2495646A1 (en) | 1980-12-08 | 1980-12-08 | YARNS AND FIBERS OF GOOD PROPERTIES BASED ON MIXING VINYL POLYHLORIDE AND SURCHLORINE VINYL POLYHLORIDE AND PROCESS FOR OBTAINING THEM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0053991A1 EP0053991A1 (en) | 1982-06-16 |
| EP0053991B1 true EP0053991B1 (en) | 1984-04-11 |
Family
ID=9248808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81420155A Expired EP0053991B1 (en) | 1980-12-08 | 1981-10-29 | Good quality filaments, threads, fibres from a mixture of atactic polyvinyl chloride and overchlorinated polyvinyl chloride, and process for their manufacture |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4780368A (en) |
| EP (1) | EP0053991B1 (en) |
| JP (1) | JPS57167412A (en) |
| AR (1) | AR231732A1 (en) |
| BR (1) | BR8108319A (en) |
| CA (1) | CA1173612A (en) |
| DE (1) | DE3163105D1 (en) |
| ES (1) | ES507734A0 (en) |
| FR (1) | FR2495646A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2524475A1 (en) * | 1982-04-01 | 1983-10-07 | Rhovyl | SOLUTIONS BASED ON VINYL POLYHLORIDE, THEIR OBTAINING PROCESS, AND THREADS AND FIBERS THUS OBTAINED |
| FR2579636B1 (en) * | 1985-03-26 | 1988-03-18 | Rhovyl | VINYL POLYCHLORIDE YARN AND FIBER DYEING PROCESS |
| FR2579637B1 (en) * | 1985-03-26 | 1988-03-18 | Rhovyl | VINYL POLYCHLORIDE YARN AND FIBER DYEING PROCESS |
| FR2680525B1 (en) * | 1991-08-23 | 1996-04-12 | Rhovyl | FIBERS BASED ON PVC / CHLORINE PVC MIXTURE HAVING IMPROVED MECHANICAL PROPERTIES AND YARNS OF FIBERS OF IMPROVED STRENGTH OBTAINED FROM SUCH FIBERS. |
| US6933024B2 (en) * | 2002-07-18 | 2005-08-23 | Hewlett-Packard Development Company, L.P. | Water soluble polymers as inkjet recording materials |
| CN103124812B (en) * | 2010-10-06 | 2015-02-11 | 株式会社钟化 | Preparation method of polyvinyl chloride resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1359178A (en) * | 1963-02-12 | 1964-04-24 | Rhovyl Sa | Synthetic fibers based on polyvinyl chloride |
| AT292177B (en) * | 1963-07-31 | 1971-08-10 | Chatillon Italiana Fibre | Process for the production of heat-shrinkable fibers from polyvinyl chloride |
| BE791829A (en) * | 1971-11-26 | 1973-05-23 | Bayer Ag | SYNDIOTACTIC POLYVINYL CHLORIDE FILAMENTS AND FIBERS |
-
1980
- 1980-12-08 FR FR8026047A patent/FR2495646A1/en active Granted
-
1981
- 1981-10-29 DE DE8181420155T patent/DE3163105D1/en not_active Expired
- 1981-10-29 EP EP81420155A patent/EP0053991B1/en not_active Expired
- 1981-12-03 CA CA000391437A patent/CA1173612A/en not_active Expired
- 1981-12-04 ES ES507734A patent/ES507734A0/en active Granted
- 1981-12-04 BR BR8108319A patent/BR8108319A/en unknown
- 1981-12-07 JP JP56196718A patent/JPS57167412A/en active Granted
- 1981-12-07 AR AR287719A patent/AR231732A1/en active
-
1986
- 1986-02-03 US US06/825,946 patent/US4780368A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3163105D1 (en) | 1984-05-17 |
| EP0053991A1 (en) | 1982-06-16 |
| FR2495646A1 (en) | 1982-06-11 |
| BR8108319A (en) | 1982-10-05 |
| AR231732A1 (en) | 1985-02-28 |
| JPS57167412A (en) | 1982-10-15 |
| FR2495646B1 (en) | 1984-03-09 |
| JPH0152487B2 (en) | 1989-11-09 |
| ES8207238A1 (en) | 1982-09-01 |
| CA1173612A (en) | 1984-09-04 |
| US4780368A (en) | 1988-10-25 |
| ES507734A0 (en) | 1982-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1991000381A1 (en) | Aramid monofilament and method for obtaining same | |
| EP0041904B1 (en) | Solutions which can be shaped, shaped articles obtained from these solutions as well as process of production of same | |
| EP0053991B1 (en) | Good quality filaments, threads, fibres from a mixture of atactic polyvinyl chloride and overchlorinated polyvinyl chloride, and process for their manufacture | |
| FR2497212A1 (en) | ACRYLIC FIBER FOR THE PRODUCTION OF PREOXIDIZED FIBER OR CARBON FIBER AND ITS MANUFACTURE | |
| EP0091384B1 (en) | Solutions of polyvinyl chloride, process for their production and yarns and fibres so obtained | |
| CA1056115A (en) | Process for making threads and fibers from poly (vinylidene fluoride)_ | |
| FR2571747A2 (en) | POLYACRYLONITRILE FIBER WITH MECHANICAL STRENGTH AND HIGH ELEVITY MODULE | |
| EP0530119B1 (en) | Fibres from a mixture of PVC and chlorinated PVC with improved mechanical properties and staple yarns with improved tenacity made from these fibres | |
| EP0053990B1 (en) | Atactic polyvinyl chloride filaments and fibres having good properties and process for their preparation | |
| CA2074262C (en) | Aramid monofilament having a lightly structured skin - process used to obtain said monofilament | |
| FR2491504A1 (en) | PROCESS FOR THE MANUFACTURE OF CARBON FIBERS AND THE PRODUCT THUS OBTAINED | |
| CA1279966C (en) | Dyeing process before spinning of polyvinyl chloride based yarns and fibers | |
| CH374633A (en) | Process for manufacturing a fibrous product with ion exchange properties | |
| CA1280565C (en) | Dyeing process after spinning of polyvinyl chloride based yarns and fibers | |
| CA1211581A (en) | Fibers and yarns made from a poly(vinyl chloride) and cellulose acetate mixture; process for preparing the same | |
| FR2524499A1 (en) | YARNS AND FIBERS BASED ON MIXTURES OF VINYL POLYHLORIDE AND ACRYLIC POLYMER AND PROCESS FOR OBTAINING THEM | |
| FR2538823A1 (en) | PROCESS FOR PRODUCING ACRYLONITRILE-BASED FIBERS, DYED IN LINE | |
| CA1173610A (en) | Cellulose and polyvinyl chloride shaped articles and process for manufacturing them | |
| BE408422A (en) | ||
| BE568898A (en) | ||
| CH294348A (en) | A process for the manufacture of shaped articles from a solution of an acrylonitrile polymer. | |
| CH435543A (en) | Textile fibers and process for their manufacture | |
| CH414056A (en) | Filiform element and method of manufacturing said element | |
| BE629827A (en) | ||
| BE408138A (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): BE CH DE GB IT NL |
|
| 17P | Request for examination filed |
Effective date: 19820702 |
|
| ITF | It: translation for a ep patent filed | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): BE CH DE GB IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 3163105 Country of ref document: DE Date of ref document: 19840517 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19980923 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19981014 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19981020 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19981023 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19981117 Year of fee payment: 18 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991029 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991031 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991031 |
|
| BERE | Be: lapsed |
Owner name: RHOVYL Effective date: 19991031 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000501 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19991029 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20000501 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000801 |