EP1453995A1 - Method for making propylene monofilaments, propylene monofilaments and their use - Google Patents

Method for making propylene monofilaments, propylene monofilaments and their use

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Publication number
EP1453995A1
EP1453995A1 EP02787899A EP02787899A EP1453995A1 EP 1453995 A1 EP1453995 A1 EP 1453995A1 EP 02787899 A EP02787899 A EP 02787899A EP 02787899 A EP02787899 A EP 02787899A EP 1453995 A1 EP1453995 A1 EP 1453995A1
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EP
European Patent Office
Prior art keywords
monofilaments
polypropylene
additive
weight
mfi
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.)
Granted
Application number
EP02787899A
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German (de)
French (fr)
Other versions
EP1453995B1 (en
Inventor
Gustav Schütze
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.)
ExNex AG
Original Assignee
Rhodia Industrial Yarns AG
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Publication date
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Publication of EP1453995A1 publication Critical patent/EP1453995A1/en
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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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the invention relates to a process for the production of polypropylene monofilaments having a melt viscosity index (MFI) 230 ° C / 2.16 kg from 2 to 16 g / 10 min, which have a diameter greater than 0.050 mm and improved abrasion resistance; it also relates to monofilaments of this polypropylene, as well as their use.
  • MFI melt viscosity index
  • Two-dimensional polypropylene textile articles are of great interest, as chemically and mechanically resistant filtration means, for filtration in the chemical, pharmaceutical and food industries.
  • relatively coarse monofilaments are required, which have a diameter greater than
  • Monofilaments of pure polypropylene have the disadvantage of forming a lot of dust due to the low resistance of this substance to abrasion during the weaving process.
  • the abrasion problem is also known for other thermoplastics.
  • PEP-A2-0 784 107 cites monofilaments spun in the molten state, of polyamide, polyester or polypropylene, intended for the fabrics of paper machines and the threads of edge trimmers.
  • abrasion resistant monofilaments are obtained using 70 to 99% by weight of fibrogenic polymer and 1 to 30% by weight of a polyethylene / polypropylene rubber, modified with maleic anhydride. , and other additives.
  • the examples are however limited, as far as the fibrogenic polymer is concerned, to polyamide 6 and to polyethylene terephthalate, as well as to a copolyamide of PA66 and PA6. Spinning speeds are not specified.
  • EP-A-1059370 a process is also known for manufacturing polypropylene multifilaments intended for textile applications.
  • an isotactic polypropylene, catalyzed by a metallocene is used, the melt viscosity index of which must be greater than 19 g for 10 minutes if the desired shrinkage characteristics are to be achieved. Indeed, to obtain a low shrinkage, high values of the MFI are necessary.
  • Yet another problem consists in making available the use of coarse monofilaments, having good abrasion resistance, for the manufacture of two-dimensional technical articles, in particular intended for filtration.
  • polypropylene use is preferably made of a homopolymer having a melt viscosity index of more than 2 g / 10 min, preferably from 6 to 13 g / 10 min, in particular from 12 to 13 g / 10 min.
  • An MFI of more than 16 g / 10 min has the drawback of giving insufficient mechanical characteristics and poor resistance to abrasion.
  • an additive consisting of a combination of lubricant, filler and thermal stabilizer.
  • lubricant 0.5 to 1.2% by weight of polyethylene waxes, calcium carbonate and hindered phenols have been found to be particularly suitable.
  • a lubricant in another variant, it is suitable to use as an additive 0.05 to 1.0% by weight, in particular 0.3 to 1.0% by weight, of a lubricant.
  • a lubricant particularly suitable as lubricants are the metal salts of carboxylic acids, linear or branched hydrocarbons, fluorinated elastomers, polydimethylsiloxanes.
  • fillers as an additive.
  • fillers 0.01 to 0.1% by weight of aerosils and 0.1 to 1.0% by weight of calcium carbonate have been found to be particularly suitable.
  • a thermal stabilizer Phenols, phosphites and sterically hindered phosphonites have been found to be particularly suitable.
  • it is suitable to use as additive 1 to 20% by weight of a polypropylene / polyethylene copolymer having a melting point> 140 ° C.
  • the monofilaments have a resistance of at least 50 cN / tex, for an elongation corresponding to the maximum tensile force (elongation at break) of less than 35%, preferably less than 30%.
  • a resistance of less than 50 cN / tex has the drawback of multiplying the breaks in the yarn during the weaving process.
  • the monofilaments have an abrasion of less than 0.05%.
  • the abrasion is greater than 0.05%, irregularities occur during weaving, due to too rapid fouling of the combs. This makes it necessary to shorten the intervals between cleanings, which decreases the productivity of the loom.
  • the monofilaments are characterized by a relative breaking energy> 100% after 24 hours treatment at 120 ° C., in particular after aging in an oven. This has the advantage of increasing the service life of the filters when they are subjected to relatively high thermal stress and to harsh chemicals.
  • the monofilaments according to the invention are particularly suitable for the manufacture of two-dimensional articles intended for filtration in the chemical, pharmaceutical and food industries.
  • melt viscosity index 230 ° C / 2.16 kg varying from 6.0 to 13.0 g / 10 minutes.
  • 50 kg of polypropylene granulate are mixed each time, using 100 kg drums and an eccentric mixer. Mixing takes place, depending on the additive, according to two different processes. The different methods are explained in the examples.
  • the granulated / additive mixture is admitted directly into the extruder and melted.
  • Spinning pump displacement: 10 cm 3 / revolutions
  • Spinning block electrically heated Titration pump 23.19 revolutions / min Dies: diameter: 0.7 mm capillary length: 3 x D
  • Drawing bench 1 7 pancakes; diameter of the pancakes: 230 mm; 1 heating channel Drawing bench 2: 7 pancakes; diameter of the pancakes: 230 mm; 1 heating channel Drawing bench 3: 7 pancakes; diameter of the pancakes: 230 mm; 2 heating channels Drawing bench 4: 4 pancakes; diameter of the pancakes: 230 mm
  • the granule is rolled for half an hour in an adhesive, such as Baysilon M 100® (trademark of the firm Bager AG), then the rest of the additives are added and mixed for an additional 1.5 hours.
  • an adhesive such as Baysilon M 100® (trademark of the firm Bager AG)
  • the mixture of granules consisting of polypropylene and modified polyolefin PP / PE is mixed for one hour, with a melting point> 140 ° C.
  • Example 1 (reference example 1): polypropylene with MFI of 13.0 g / 10 min
  • Example 2 MFI polypropylene of 6.0 g / 10 min, with a combination as an additive
  • Example 3 (reference example 2): polypropylene with MFI of 12.0 g / 10 min
  • Example 4 Polypropylene with MFI of 12.0 g / 10 min, with PP / PE with melting point> 140 ° C as additive
  • Example 5 polypropylene with MFI of 13.0 g / 10 min, with a lubricant as an additive
  • Example 6 polypropylene with MFI of 13.0 g / 10 min, with a combination based on thermal stabilizers as an additive
  • Example 7 polypropylene with MFI of 13.0 g / 10 min, with a combination as an additive
  • Example 8 Polypropylene with MFI of 13.0 g / 10 min, with anti-gas fading stabilization
  • Example 9 MFI polypropylene of 9.0 g / 10 min, with anti-gas fading stabilization
  • Fig. 3b shows photographs representing the state of the combs of a weaving loom after manufacturing 100 m, 200 m and 300 m of fabric using the monofilament according to the invention [exemplary embodiment (example 8)]. Even after manufacturing 300 m of fabric, the amount of down produced remains lower than that obtained for 100 m in the reference example.
  • CM The mechanical constant CM is calculated according to the following formula: where D denotes the elongation in [%] and F denotes the resistance in [cN / tex].
  • the sectional beams of 1000 m each, were manufactured using the monofilaments of
  • the weaving tests are carried out on a ribbon loom.
  • the crowd is formed thanks to eccentrics.
  • Working mode without weft re-entry
  • Comb opening: 0.175 mm thickness of teeth: 0.264 mm width of teeth: 7.0 mm Rotation speed of the loom: 1000 rpm
  • the combs are photographed after an operating time of 100 m or 200 m, preferably 300 m, and they are assigned a classification.
  • the monofilaments according to the invention which have a diameter> 0.050 mm, are suitable for the manufacture, without abrasion, of fabrics intended for filtration.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Woven Fabrics (AREA)

Abstract

The invention concerns a method for making propylene monofilaments having a 230 °C/2.16 kg melt flow index (MFI) from 2 to 16 g/10 min, having a diameter larger than 0.050 mm and improved abrasion resistance, which consists in adding to the polypropylene 20 to 0.1 wt. % of an additive upstream of the extruder, spinning the molten material in a water bath, drawing it and winding it. The invention also concerns a polypropylene monofilament having a 230 °C/2.6 kg melt flow index (MFI) from 2 to 16 g/10 min, having a diameter greater than 0.050 mm and improved abrasion resistance, exhibiting a strength of at least 50 cN/tex, for an elongation corresponding to the maximum tensile stress (elongation at rupture) of at least 30 %. Furthermore, it has an abrasion of less than 0.05 % and a relative tensile energy absorption > 100 % after being treated for 24 hours at 120 °C.

Description

PROCEDE DE FABRICATION DE MONOFILAMENTS DE POLYPROPYLENE, PROCESS FOR PRODUCING POLYPROPYLENE MONOFILAMENTS,
MONOFILAMENTS DE POLYPROPYLENE ET LEUR UTILISATIONPOLYPROPYLENE MONOFILAMENTS AND THEIR USE
L'invention concerne un procédé de fabrication de monofilaments d'un polypropylène présentant un indice de viscosité en fondu (MFI) 230 °C/2,16 kg de 2 à 16 g/10 min, qui possèdent un diamètre supérieur à 0,050 mm et une résistance à l'abrasion améliorée; elle concerne également des monofilaments de ce polypropylène, ainsi que leur utilisation.The invention relates to a process for the production of polypropylene monofilaments having a melt viscosity index (MFI) 230 ° C / 2.16 kg from 2 to 16 g / 10 min, which have a diameter greater than 0.050 mm and improved abrasion resistance; it also relates to monofilaments of this polypropylene, as well as their use.
Les articles textiles à deux dimensions en polypropylène sont d'un grand intérêt, en tant que moyens de filtration résistant chimiquement et mécaniquement, pour la filtration dans les industries chimique, pharmaceutique et alimentaire. Dans ce domaine, on demande surtout des monofilaments relativement grossiers, qui possèdent un diamètre supérieur àTwo-dimensional polypropylene textile articles are of great interest, as chemically and mechanically resistant filtration means, for filtration in the chemical, pharmaceutical and food industries. In this area, relatively coarse monofilaments are required, which have a diameter greater than
0,050 mm.0.050 mm.
Les monofilaments de polypropylène pur présentent l'inconvénient de former beaucoup de poussières par suite de la faible résistance de cette substance à l'abrasion lors du processus de tissage. Le problème de l'abrasion est connu également pour d'autres thermoplastiques. C'est ainsi que PEP-A2-0 784 107 cite des monofils filés à l'état fondu, de polyamide, polyester ou polypropylène, destinés aux toiles des machines à papier et aux fils des coupe-bordures. Selon ce brevet, on obtient des monofilaments résistant à l'abrasion à l'aide de 70 à 99 % en poids de polymère fibrogène et de 1 à 30 % en poids d'un caoutchouc de polyéthylène/polypropylène, modifié à l'anhydride maléique, et d'autres additifs. Les exemples se limitent toutefois, en ce qui concerne le polymère fibrogène, au polyamide 6 et au polyéthylènetéréphtalate, ainsi qu'à un copolyamide de PA66 et de PA6. Les vitesses de filage ne sont pas précisées.Monofilaments of pure polypropylene have the disadvantage of forming a lot of dust due to the low resistance of this substance to abrasion during the weaving process. The abrasion problem is also known for other thermoplastics. This is how PEP-A2-0 784 107 cites monofilaments spun in the molten state, of polyamide, polyester or polypropylene, intended for the fabrics of paper machines and the threads of edge trimmers. According to this patent, abrasion resistant monofilaments are obtained using 70 to 99% by weight of fibrogenic polymer and 1 to 30% by weight of a polyethylene / polypropylene rubber, modified with maleic anhydride. , and other additives. The examples are however limited, as far as the fibrogenic polymer is concerned, to polyamide 6 and to polyethylene terephthalate, as well as to a copolyamide of PA66 and PA6. Spinning speeds are not specified.
Grâce à l'EP-A-1059370, on connaît également un procédé de fabrication de multifilaments de polypropylène destinés à des applications textiles. Comme matériau de départ, on utilise un polypropylène isotactique, catalysé par un métallocène, dont l'indice de viscosité en fondu doit être supérieur à 19 g pour 10 minutes si l'on veut atteindre les caractéristiques de retrait souhaitées. En effet, pour obtenir un faible retrait, des valeurs élevées du MFI sont nécessaires. On trouve décrits des multifilaments FOY (Fully Oriented Yarns [≈ fils totalement orientés]) de 10 dpf (= denier par filament) [0,03953 mm] et POY (Partially Oriented Yarns [= fils partiellement orientés]) de 2 dpf (= deniers par fibre) [0,01768 mm]. En ce qui concerne les fils fabriqués, seules figurent des indications générales. On ne trouve pas décrits de monofilaments. Le problème de l'invention consiste à mettre à disposition un procédé économique de fabrication de monofilaments grossiers de polypropylène, résistant à l'abrasion. Un autre problème de l'invention consiste à fabriquer des monofilaments grossiers de polypropylène, qui présentent une résistance améliorée vis-à-vis de l'abrasion lors du tissage.Thanks to EP-A-1059370, a process is also known for manufacturing polypropylene multifilaments intended for textile applications. As the starting material, an isotactic polypropylene, catalyzed by a metallocene, is used, the melt viscosity index of which must be greater than 19 g for 10 minutes if the desired shrinkage characteristics are to be achieved. Indeed, to obtain a low shrinkage, high values of the MFI are necessary. We find described multifilaments FOY (Fully Oriented Yarns) of 10 dpf (= denier per filament) [0.03953 mm] and POY (Partially Oriented Yarns [= partially oriented yarns]) of 2 dpf (= deniers per fiber) [0.01768 mm]. With regard to the yarns produced, only general information is given. No described monofilaments are found. The problem of the invention is to provide an economical process for manufacturing coarse abrasion resistant polypropylene monofilaments. Another problem of the invention consists in manufacturing coarse polypropylene monofilaments, which have an improved resistance to abrasion during weaving.
Un autre problème encore consiste à mettre à disposition l'utilisation de monofilaments grossiers, possédant une bonne résistance à l'abrasion, pour la fabrication d'articles techniques à deux dimensions, notamment destinés à la filtration.Yet another problem consists in making available the use of coarse monofilaments, having good abrasion resistance, for the manufacture of two-dimensional technical articles, in particular intended for filtration.
Le problème est résolu selon l'invention grâce au fait que l'on ajoute au polypropylèneThe problem is solved according to the invention thanks to the fact that polypropylene is added
20 à 0,01 % en poids d'un additif en amont de l'extrudeuse, on file la matière fondue dans un bain d'eau, on l'étiré et on la bobine.20 to 0.01% by weight of an additive upstream of the extruder, the melted material is spun in a water bath, it is stretched and it is wound.
Comme polypropylène, on utilise de préférence un homopolymère possédant un indice de viscosité en fondu de plus de 2 g/10 min, de préférence de 6 à 13 g/10min, en particulier de 12 à 13 g/10 min. Un MFI de plus de 16 g/10 min présente l'inconvénient de donner des caractéristiques mécaniques insuffisantes et une mauvaise résistance à l'abrasion.As polypropylene, use is preferably made of a homopolymer having a melt viscosity index of more than 2 g / 10 min, preferably from 6 to 13 g / 10 min, in particular from 12 to 13 g / 10 min. An MFI of more than 16 g / 10 min has the drawback of giving insufficient mechanical characteristics and poor resistance to abrasion.
II est approprié d'utiliser un additif constitué d'une combinaison de lubrifiant, charge et stabilisant thermique. Comme combinaison de lubrifiant, charge et stabilisant thermique, 0,5 à 1 ,2 % en poids de cires de polyéthylène, de carbonate de calcium et de phénols à encombrement stérique se sont révélés convenir particulièrement.It is appropriate to use an additive consisting of a combination of lubricant, filler and thermal stabilizer. As a combination of lubricant, filler and thermal stabilizer, 0.5 to 1.2% by weight of polyethylene waxes, calcium carbonate and hindered phenols have been found to be particularly suitable.
Dans une autre variante, il est approprié d'utiliser comme additif 0,05 à 1 ,0 % en poids, en particulier 0,3 à 1 ,0 % en poids, d'un lubrifiant. Conviennent particulièrement, comme lubrifiant, les sels métalliques des acides carboxyliques, les hydrocarbures linéaires ou ramifiés, les élastomères fluorés, les polydiméthylsiloxanes.In another variant, it is suitable to use as an additive 0.05 to 1.0% by weight, in particular 0.3 to 1.0% by weight, of a lubricant. Particularly suitable as lubricants are the metal salts of carboxylic acids, linear or branched hydrocarbons, fluorinated elastomers, polydimethylsiloxanes.
Dans une autre variante encore, il est approprié d'utiliser comme additif des charges.In yet another variant, it is appropriate to use fillers as an additive.
Comme charges, 0,01 à 0,1 % en poids d'aérosils et 0,1 à 1 ,0 % en poids de carbonate de calcium se sont révélés convenir particulièrement.As fillers, 0.01 to 0.1% by weight of aerosils and 0.1 to 1.0% by weight of calcium carbonate have been found to be particularly suitable.
Dans une autre variante encore, il est approprié d'utiliser comme additif 0,1 à 0,8 % en poids d'un stabilisant thermique. Les phénols, les phosphites et les phosphonites à encombrement stérique se sont révélés convenir particulièrement. Dans une autre variante encore, il est approprié d'utiliser comme additif 1 à 20 % en poids d'un copolymère de polypropylène/polyéthylène possédant un point de fusion > 140 °C.In yet another variant, it is suitable to use as an additive 0.1 to 0.8% by weight of a thermal stabilizer. Phenols, phosphites and sterically hindered phosphonites have been found to be particularly suitable. In yet another variant, it is suitable to use as additive 1 to 20% by weight of a polypropylene / polyethylene copolymer having a melting point> 140 ° C.
Il est approprié que les monofilaments possèdent une résistance d'au moins 50 cN/tex, pour un allongement correspondant à l'effort de traction maximal (allongement à la rupture) de moins de 35 %, de préférence moins de 30 %. En effet, une résistance inférieure à 50 cN/tex présente l'inconvénient de multiplier les casses de fil lors du processus de tissage.It is appropriate that the monofilaments have a resistance of at least 50 cN / tex, for an elongation corresponding to the maximum tensile force (elongation at break) of less than 35%, preferably less than 30%. In fact, a resistance of less than 50 cN / tex has the drawback of multiplying the breaks in the yarn during the weaving process.
Il est par ailleurs important que les monofilaments présentent une abrasion de moins de 0,05 %. En effet, lorsque l'abrasion est supérieure à 0,05 %, il se produit des irrégularités lors du tissage, dues à un encrassement trop rapide des peignes. Cela oblige à raccourcir les intervalles entre nettoyages, ce qui diminue la productivité du métier.It is also important that the monofilaments have an abrasion of less than 0.05%. In fact, when the abrasion is greater than 0.05%, irregularities occur during weaving, due to too rapid fouling of the combs. This makes it necessary to shorten the intervals between cleanings, which decreases the productivity of the loom.
Il est approprié que les monofilaments se caractérisent par une énergie de rupture relative > 100 % après traitement de 24 heures à 120 °C, en particulier après vieillissement en étuve. Cela offre l'avantage d'accroître la durée de vie des filtres, lorsqu'ils sont soumis à une sollicitation thermique relativement forte et à des produits chimiques agressifs.It is appropriate that the monofilaments are characterized by a relative breaking energy> 100% after 24 hours treatment at 120 ° C., in particular after aging in an oven. This has the advantage of increasing the service life of the filters when they are subjected to relatively high thermal stress and to harsh chemicals.
Les monofilaments selon l'invention conviennent particulièrement à la fabrication d'articles à deux dimensions destinés à la filtration dans les industries chimique, pharmaceutique et alimentaire.The monofilaments according to the invention are particularly suitable for the manufacture of two-dimensional articles intended for filtration in the chemical, pharmaceutical and food industries.
On va maintenant décrire l'invention de façon plus détaillée, à l'aide d'exemples.The invention will now be described in more detail, using examples.
PolymèrePolymer
Comme polymères fibrogènes, on a utilisé lors des essais cinq polypropylènes différents, en vente dans le commerce, dont l'indice de viscosité en fondu (MFI) 230 °C/2,16 kg varie de 6,0 à 13,0 g/10 min. On mélange chaque fois 50 kg de granulé de polypropylène, en utilisant des fûts de 100 kg et un mélangeur excentrique. Le mélangeage s'effectue, en fonction de l'additif, selon deux procédés différents. Les différents procédés sont expliqués dans les exemples. Le mélange granulé/additif est admis directement dans l'extrudeuse et fondu. Conditions de filage Extrudeuse : diamètre : 40 mm; longueur du cylindre : L/D = 25As fibrogenic polymers, five different commercially available polypropylenes were used in the tests, the melt viscosity index (MFI) 230 ° C / 2.16 kg varying from 6.0 to 13.0 g / 10 minutes. 50 kg of polypropylene granulate are mixed each time, using 100 kg drums and an eccentric mixer. Mixing takes place, depending on the additive, according to two different processes. The different methods are explained in the examples. The granulated / additive mixture is admitted directly into the extruder and melted. Spinning conditions Extruder: diameter: 40 mm; cylinder length: L / D = 25
Pression de l'extrudeuse : 80 bar débit : 19,76 kg/h 5 zones chauffantesExtruder pressure: 80 bar flow rate: 19.76 kg / h 5 heating zones
Pompe de filage : cylindrée : 10 cm3/tours Bloc de filage : à chauffage électrique Pompe de titrage 23,19 tours/min Filières : diamètre : 0,7 mm longueur du capillaire : 3 x DSpinning pump: displacement: 10 cm 3 / revolutions Spinning block: electrically heated Titration pump 23.19 revolutions / min Dies: diameter: 0.7 mm capillary length: 3 x D
Bain d'eau : distance entre filière et bain d'eau : 45 mm température : 30 °CWater bath: distance between die and water bath: 45 mm temperature: 30 ° C
Bancs d'étirage et canaux de chauffageDrawing benches and heating channels
Banc d'étirage 1 : 7 galettes; diamètre des galettes : 230 mm; 1 canal de chauffage Banc d'étirage 2 : 7 galettes; diamètre des galettes : 230 mm; 1 canal de chauffage Banc d'étirage 3 : 7 galettes; diamètre des galettes : 230 mm; 2 canaux de chauffage Banc d'étirage 4 : 4 galettes; diamètre des galettes : 230 mmDrawing bench 1: 7 pancakes; diameter of the pancakes: 230 mm; 1 heating channel Drawing bench 2: 7 pancakes; diameter of the pancakes: 230 mm; 1 heating channel Drawing bench 3: 7 pancakes; diameter of the pancakes: 230 mm; 2 heating channels Drawing bench 4: 4 pancakes; diameter of the pancakes: 230 mm
Préparation de filage solution aqueuse à 5 %Preparation of spinning 5% aqueous solution
Préparation des échantillonsSample preparation
Exemples 2, 5, 6 et 7Examples 2, 5, 6 and 7
Dans le cas des additifs pulvérulents, tels que charges, lubrifiant, stabilisant thermique, etc., on commence par rouler pendant une demi-heure le granulé dans un adhésif, tel que Baysilon M 100® (marque commerciale de la firme Bager AG), puis on ajoute le reste des additifs et l'on mélange pendant 1 ,5 heure de plus.In the case of pulverulent additives, such as fillers, lubricant, thermal stabilizer, etc., the granule is rolled for half an hour in an adhesive, such as Baysilon M 100® (trademark of the firm Bager AG), then the rest of the additives are added and mixed for an additional 1.5 hours.
Exemple 4Example 4
Dans le cas des polyoléfines modifiées, on mélange pendant une heure le mélange de granulés constitué de polypropylène et de polyolefine modifiée PP/PE, à point de fusion > 140 °C.In the case of modified polyolefins, the mixture of granules consisting of polypropylene and modified polyolefin PP / PE is mixed for one hour, with a melting point> 140 ° C.
Les exemples ont été résumés au Tableau 1. Tableau 1The examples have been summarized in Table 1. Table 1
* Énergie de rupture en pourcentage de la valeur initiale* Breaking energy as a percentage of the initial value
Exemple 1 (exemple de référence 1) : polypropylène à MFI de 13,0 g/10 minExample 1 (reference example 1): polypropylene with MFI of 13.0 g / 10 min
Exemple 2 : polypropylène à MFI de 6,0 g/10 min, avec une combinaison comme additifExample 2: MFI polypropylene of 6.0 g / 10 min, with a combination as an additive
Exemple 3 (exemple de référence 2) : polypropylène à MFI de 12,0 g/10 minExample 3 (reference example 2): polypropylene with MFI of 12.0 g / 10 min
Exemple 4 : polypropylène à MFI de 12,0 g/10 min, avec du PP/PE à point de fusion > 140 °C comme additifExample 4: Polypropylene with MFI of 12.0 g / 10 min, with PP / PE with melting point> 140 ° C as additive
Exemple 5 : polypropylène à MFI de 13,0 g/10 min, avec un lubrifiant comme additifExample 5: polypropylene with MFI of 13.0 g / 10 min, with a lubricant as an additive
Exemple 6 : polypropylène à MFI de 13,0 g/10 min, avec une combinaison à base de stabilisants thermiques comme additifExample 6: polypropylene with MFI of 13.0 g / 10 min, with a combination based on thermal stabilizers as an additive
Exemple 7 : polypropylène à MFI de 13,0 g/10 min, avec une combinaison comme additifExample 7: polypropylene with MFI of 13.0 g / 10 min, with a combination as an additive
Exemple 8 : polypropylène à MFI de 13,0 g/10 min, avec stabilisation anti-gas fadingExample 8: Polypropylene with MFI of 13.0 g / 10 min, with anti-gas fading stabilization
Exemple 9 : polypropylène à MFI de 9,0 g/10 min, avec stabilisation anti-gas fading Example 9: MFI polypropylene of 9.0 g / 10 min, with anti-gas fading stabilization
Pour permettre des explications plus détaillées, on a représenté les résultats graphiquementTo allow more detailed explanations, the results are represented graphically
olonnes indiquant l'énergie de rupture spécifique, le n fonction de l'addition d'un additif selon l'exemple 2; columns indicating the specific breaking energy, the n function of the addition of an additive according to Example 2;
l'abrasion en fonction de l'addition d'un additif seloabrasion depending on the addition of a selo additive
l'abrasion en fonction de l'addition d'un additif et d référence (exemple 1); l'abrasion en fonction de l'addition d'un additif et du réalisation (exemple 8).abrasion depending on the addition of an additive and d reference (Example 1); abrasion depending on the addition of an additive and the embodiment (example 8).
auche représente l'énergie de rupture spécifique, celle t celle de droite l'abrasion, en fonction de l'addition d'un es de gauche reflètent l'état de la technique, celles de enus avec les monofilaments selon l'invention. Cette rne l'abrasion, une amélioration de plus de 100 %. Or, t au minimum une durée de fonctionnement deux fois vant qu'il ne faille le nettoyer. On obtient des résultats elative. Ici, la colonne de droite de la paire de colonnes du milieu fait également apparaître une amélioration de plus de 50 %. L'énergie de rupture auche represents the specific breaking energy, that t that of abrasion on the right, depending on the addition of a left es reflect the state of the art, those of enus with the monofilaments according to the invention. This leads to abrasion, an improvement of over 100%. However, t at least twice the operating time before it has to be cleaned. We get results elative. Here, the right column of the middle column pair also shows an improvement of more than 50%. The breaking energy
La Fig. 3b montre des photographies représentant l'état des peignes d'un métier à tisser après fabrication de 100 m, 200 m et 300 m de tissu à l'aide du monofilament selon l'invention [exemple de réalisation (exemple 8)]. Même après fabrication de 300 m de tissu , la quantité de duvet produite reste inférieure à celle obtenue pour 100 m dans l'exemple de référence.Fig. 3b shows photographs representing the state of the combs of a weaving loom after manufacturing 100 m, 200 m and 300 m of fabric using the monofilament according to the invention [exemplary embodiment (example 8)]. Even after manufacturing 300 m of fabric, the amount of down produced remains lower than that obtained for 100 m in the reference example.
Méthodes de mesure :Measuring methods:
• Indice de viscosité en fondu selon ASTM D1238 • Détermination du titre selon SN 197 012 et SN 197 015, complétées par DIN 53830• Melt viscosity index according to ASTM D1238 • Determination of the titer according to SN 197 012 and SN 197 015, supplemented by DIN 53830
• Le calcul de la constante mécanique CM est réalisé selon la formule suivante : où D désigne l'allongement en [%] et F la résistance en [cN/tex].• The mechanical constant CM is calculated according to the following formula: where D denotes the elongation in [%] and F denotes the resistance in [cN / tex].
Description des essais d'abrasionDescription of abrasion tests
Fabrication des ensouples sectionnellesManufacturing of sectional beams
Les ensouples sectionnelles, de 1000 m chacune, ont été fabriquées à l'aide des monofils deThe sectional beams, of 1000 m each, were manufactured using the monofilaments of
80 bobines des différentes variantes.80 reels of different variants.
Essais de tissageWeaving trials
Les essais de tissage sont réalisés sur un métier à rubans.The weaving tests are carried out on a ribbon loom.
Production maximale possible : 4000 tours/minMaximum possible production: 4000 rpm
La foule est formée grâce à des excentriques. Mode de travail : sans rentrée de trameThe crowd is formed thanks to eccentrics. Working mode: without weft re-entry
Densité des fils de chaîne : 22,80 fils/cmDensity of warp threads: 22.80 threads / cm
Peigne : ouverture : 0,175 mm épaisseur des dents : 0,264 mm largeur des dents : 7,0 mm Vitesse de rotation du métier à tisser : 1000 tours/minComb: opening: 0.175 mm thickness of teeth: 0.264 mm width of teeth: 7.0 mm Rotation speed of the loom: 1000 rpm
Vitesse de tissage : 10 m/hWeaving speed: 10 m / h
Armure : toile à draps L1/1Weave: L1 / 1 cloth
Évaluation du comportement à l'abrasion : - évaluation visuelle des peignesAssessment of abrasion behavior: - visual assessment of combs
- détermination gravimétrique de la quantité de duvet produite Lors de l'examen visuel, on photographie les peignes après une durée de fonctionnement de 100 m ou 200 m, de préférence de 300 m, et on leur attribue un classement.- gravimetric determination of the quantity of down produced During the visual examination, the combs are photographed after an operating time of 100 m or 200 m, preferably 300 m, and they are assigned a classification.
L'évaluation du comportement à l'abrasion selon la méthode gravimétrique est décrite ci- dessous. Pour cela, on recueille la totalité du duvet formé, après une durée de fonctionnement de 300 m, on la pèse et on la rapporte au poids des fils de chaîne à l'aide de la formule suivante :The evaluation of the abrasion behavior according to the gravimetric method is described below. To do this, the entire down formed is collected, after an operating time of 300 m, it is weighed and it is related to the weight of the warp threads using the following formula:
dépôt en % deposit in%
Les monofilaments selon l'invention, qui possèdent un diamètre > 0,050 mm, conviennent à la fabrication, sans abrasion, des tissus destinés à la filtration.The monofilaments according to the invention, which have a diameter> 0.050 mm, are suitable for the manufacture, without abrasion, of fabrics intended for filtration.
Grâce au procédé selon l'invention et au monofilament selon l'invention, on est parvenu pour la première fois à tisser pratiquement sans abrasion du monofilament de polypropylène et à accroître considérablement la durée de fonctionnement du métier à tisser. Ce monofilament convient particulièrement à la fabrication des tissus qui sont utilisés pour la filtration dans les industries chimique, pharmaceutique et alimentaire. Thanks to the process according to the invention and to the monofilament according to the invention, it has been possible for the first time to weave practically without abrasion of the polypropylene monofilament and to considerably increase the operating time of the loom. This monofilament is particularly suitable for the manufacture of fabrics which are used for filtration in the chemical, pharmaceutical and food industries.

Claims

REVENDICATIONS
1. Procédé de fabrication de monofilaments d'un polypropylène présentant un indice de viscosité en fondu (MFI) 230 °C/2,16 kg de 2 à 16 g/10 min, possédant un diamètre supérieur à 0,050 mm et une résistance à l'abrasion améliorée, caractérisé en ce que l'on ajoute au polypropylène 20 à 0,01 % en poids d'un additif en amont de l'extrudeuse, on file la matière fondue dans un bain d'eau, on l'étiré et on la bobine.1. Process for the production of polypropylene monofilaments having a melt viscosity index (MFI) 230 ° C / 2.16 kg from 2 to 16 g / 10 min, having a diameter greater than 0.050 mm and a resistance to l improved abrasion, characterized in that 20 to 0.01% by weight of an additive is added to the polypropylene upstream of the extruder, the melt is spun into a water bath, it is stretched and we reel it.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise comme additif 0,5 à 1 ,2 % en poids d'une combinaison de lubrifiant, charge et stabilisant thermique.2. Method according to claim 1, characterized in that one uses as additive 0.5 to 1.2% by weight of a combination of lubricant, filler and thermal stabilizer.
3. Procédé selon la revendication 1 , caractérisé en ce que l'on utilise comme additif 0,05 à 1,0 % en poids d'un lubrifiant.3. Method according to claim 1, characterized in that one uses as additive 0.05 to 1.0% by weight of a lubricant.
4. Procédé selon la revendication 1, caractérisé en ce que l'on utilise comme additif 0,01 à 1 ,0 % en poids de charges.4. Method according to claim 1, characterized in that one uses as additive 0.01 to 1.0% by weight of fillers.
5. Procédé selon la revendication 1 , caractérisé en ce que l'on utilise comme additif 0,1 à 0,8 % en poids d'un stabilisant thermique.5. Method according to claim 1, characterized in that one uses as an additive 0.1 to 0.8% by weight of a thermal stabilizer.
6. Procédé selon la revendication 1 , caractérisé en ce que l'on utilise comme additif 1 à 20 % en poids d'un copolymère de polypropylène/polyéthylène possédant un point de fusion > 140 °C.6. Method according to claim 1, characterized in that one uses as additive 1 to 20% by weight of a polypropylene / polyethylene copolymer having a melting point> 140 ° C.
7. Monofilaments d'un polypropylène présentant un indice de viscosité en fondu (MFI) 230 °C/2,16 kg de 2 à 16 g/10 min, possédant un diamètre supérieur à 0,050 mm et une résistance à l'abrasion améliorée, caractérisés par une résistance d'au moins 50 cN/tex, pour un allongement correspondant à l'effort de traction maximal (allongement à la rupture) de moins de 35 %, de préférence moins de 30 %.7. Polypropylene monofilaments having a melt viscosity index (MFI) 230 ° C / 2.16 kg from 2 to 16 g / 10 min, having a diameter greater than 0.050 mm and an improved abrasion resistance, characterized by a resistance of at least 50 cN / tex, for an elongation corresponding to the maximum tensile force (elongation at break) of less than 35%, preferably less than 30%.
8. Monofilaments selon la revendication 7, caractérisés par une abrasion de moins de 0,05 %.8. Monofilaments according to claim 7, characterized by an abrasion of less than 0.05%.
9. Monofilaments selon la revendication 7, caractérisés par une énergie de rupture relative > 100 % après traitement de 24 heures à 120 °C. 9. Monofilaments according to claim 7, characterized by a relative breaking energy> 100% after 24 hours treatment at 120 ° C.
0. Utilisation des monofilaments selon les revendications 7 à 9 pour la fabrication d'articles à deux dimensions destinés à la filtration dans les industries chimique, pharmaceutique et alimentaire. 0. Use of the monofilaments according to claims 7 to 9 for the manufacture of two-dimensional articles intended for filtration in the chemical, pharmaceutical and food industries.
EP02787899A 2001-12-05 2002-12-03 Method for making propylene monofilaments, propylene monofilaments and their use Expired - Lifetime EP1453995B1 (en)

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CH22162001 2001-12-05
PCT/EP2002/013649 WO2003048434A1 (en) 2001-12-05 2002-12-03 Method for making propylene monofilaments, propylene monofilaments and their use

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FR2868437B1 (en) * 2004-03-30 2006-05-26 Rhodia Chimie Sa MONOFILAMENTS BASED ON POLYPROPYLENE WITH IMPROVED PROPERTIES
WO2006028908A1 (en) 2004-09-08 2006-03-16 E.I. Dupont De Nemours And Company Ethylene copolymer modified polypropylene and shaped articles
JP4860483B2 (en) 2004-11-26 2012-01-25 三井化学株式会社 Polypropylene nonwoven fabric and its use
CN100357505C (en) * 2005-06-27 2007-12-26 江苏泽天化纤有限公司 High strength and low extending thick Denier polypropylene yarns and production thereof
KR100752500B1 (en) * 2006-09-08 2007-08-27 주식회사 휴비스 Fabric for clothes which have easy packing property and smooth out wrinkles easily
CN101851796B (en) * 2009-03-31 2012-05-30 中国水产科学研究院东海水产研究所 Method for processing wearable blended and modified polypropylene monofilaments for manufacturing fishing rope
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DE60223714T2 (en) 2008-10-30
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