EP0658222A1 - Process for producing soil-repellent and abrasion-resistant monofilaments and their use - Google Patents

Process for producing soil-repellent and abrasion-resistant monofilaments and their use

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Publication number
EP0658222A1
EP0658222A1 EP94917779A EP94917779A EP0658222A1 EP 0658222 A1 EP0658222 A1 EP 0658222A1 EP 94917779 A EP94917779 A EP 94917779A EP 94917779 A EP94917779 A EP 94917779A EP 0658222 A1 EP0658222 A1 EP 0658222A1
Authority
EP
European Patent Office
Prior art keywords
monofilament
repellent
abrasion
soiling
resistant
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.)
Withdrawn
Application number
EP94917779A
Other languages
German (de)
French (fr)
Inventor
Halim Baris
Etienne Fleury
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
Rhone Poulenc Viscosuisse SA
Societe de la Viscose Suisse SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Viscosuisse SA, Societe de la Viscose Suisse SA filed Critical Rhone Poulenc Viscosuisse SA
Publication of EP0658222A1 publication Critical patent/EP0658222A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • C08G63/6956—Dicarboxylic acids and dihydroxy compounds
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • 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
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • 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
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • the invention relates to a process for the preparation of dirt-repellent and abrasion-resistant monofilaments with a diameter of 0.1 to 1.0 mm, from a linear polyethylene terephthalate / polydialkylsiloxane for the production of screen fabrics, and monofilaments for their use.
  • Solid-repellent properties for paper machine screens are understood to mean wet soiling, which also requires resistance to hydrolysis.
  • the dirt repellency is intended to extend the cleaning cycles of a sieve, the cleaning work being carried out under a high-pressure water jet and, if necessary, with a brush.
  • Dirt-repellent monofilaments are processed into technical fabrics, which are used in the wet section, in the press and dryer sections of a paper machine. Such screens are exposed to moisture and temperatures well above 100 ° C, as well as to increased mechanical stress when cleaning. Pure polyester monofilaments have disadvantages because of their dirtiness, susceptibility to hydrolysis or their relative brittleness. By adding additives in the form of stabilizers, an improvement in the resistance to hydrolysis was achieved. The increase in
  • “Abrasion-resistant” monofilaments are understood to mean those monofilaments in which no weight loss measurable in practice and no or only slight fibrillation are found in the fibrillation test.
  • copolyesters which are modified with siloxanes are eminently suitable for the abovementioned field of application, since their surface characteristics can be easily modified thanks to better sliding properties and a lower coefficient of friction, which significantly reduces the brittleness and the Dirt repellency is significantly improved.
  • the fabric can easily be post-treated.
  • Polyester / polydimethylsiloxanes which are either in granular form or are modified by addition immediately before extrusion, have proven to be particularly suitable.
  • Polyoxisilanes of the type which are modified polyesters and which are provided as starting material for the use according to the invention are known from US Pat. No. 5,123,392.
  • the known chemically modified polymers are used for the production of hydrophilic staple fibers, but should also be able to be used for fabrics made from filament yarns.
  • the hydrophilic properties enable moisture to be absorbed quickly and are therefore used primarily in a mixture with cotton and wool.
  • yarns with the stated hydrophilic properties are unsuitable in the present form for paper machine screens or fishing lines.
  • EP-A-0 269 023 also discloses silicone-modified polyesters which are suitable for producing fibers.
  • silicone units are formed in a polyester matrix. These silicone units migrate into air during extrusion and into the outer casing of the filament during stretching. The surface obtained acts like a hydrophobic film.
  • the cross-sectional chemical composition is not homogeneous.
  • the object of the invention is to provide a dirt-repellent and abrasion-resistant monofilament which is homogeneous in cross-section and which meets the high demands of a technical fabric with regard to its chemical, dirt-repellent, mechanical and abrasion-resistant properties and is used particularly in the paper industry.
  • the object is achieved according to the invention in that 0.15-5.0% by weight of polydialkylsiloxane by co-condensation, i.e. during the polycondensation; be built into the chain of the polymer.
  • the tenacity of the monofilaments is higher than 36 cN / tex, with an elongation of ⁇ 44%, based on the unstretched filament, the key feature being surprisingly good dirt repellency and low fibrillation.
  • the dirt repellency was determined as the soiling index with ⁇ 10 after 5 soiling / washout cycles, compared to> 14 ' for a polyester filament without polydimethylsiloxane.
  • polyester which consists of at least 85% by weight of polyethylene terephthalate and a polydialkylsiloxane, the polyethylene
  • ERSA ⁇ ZBLA ⁇ (RULE 26 terephthalate / polydialkylsiloxane in the finished monofilament contains 0.05 to 2% by weight, preferably 0.1 to 1.0% by weight of silicon, based on the polymer, and the homogeneous mixture is extruded into a monofilament. As . It should be emphasized that the monofilament produced has a homogeneous composition over the entire cross section.
  • a polyethylene terephthalate which has an intrinsic viscosity of> 0.60 dl / g is suitable.
  • copolymers used are preferably difunctional polydiorganosiloxanes of the general formula:
  • R1, R2 represent the same or different radicals having 2 to 20 carbon atoms.
  • PDMS Polydimethylsiloxanes
  • the silicon content in the monofilament is 0.05 to 2.0% by weight, in particular 0.1 to 2% by weight, preferably 0.1 to 1.0% by weight.
  • the polymer is prepared in a known manner by transesterification of dimethyl terephthalate and ethylene glycol and addition of 3.9% by weight of polydimethylsiloxane (PDMS) and manganese acetate in a stirred autoclave at 160 to 230 ° C, the resulting methanol distilling off quantitatively.
  • the subsequent polycondensation is carried out in the temperature range from 245 to 285 ° C using an antimony catalyst for 200 min, in a first step under progressive vacuum (1000 -> 50 bar) for 40 min and in a second step in a high vacuum ( ⁇ 1mbar) is condensed.
  • the polyethylene terephthalate / polydimethylsiloxane (PET / PDMS) is melted at a temperature of 290 ° C.
  • the extrusion takes place via a spinneret with 13 capillaries and a capillary diameter of 1.8 mm with a polymer throughput of 486 g / min.
  • the extruded monofilaments are cooled in a water bath at 70 ° C. After cooling, the monofilaments are spin-prepared and stretched to a residual elongation of approximately ⁇ 44%, relaxed and wound up at a speed of 100 m / min.
  • the resulting thread has a soiling coefficient after five treatments of less than 10 ( ⁇ 10), has a tensile strength (Ft) of 36.1 cN / tex with an elongation (Dt) of 38.8% at a stretch of 500%, based on the unstretched monofilament.
  • Ft tensile strength
  • Dt elongation
  • PET / PDMS polydimethylsiloxane
  • AI - [DL *] / L * 0 x 100
  • ERS ⁇ ZBLA ⁇ T (RULE 26) struck against a standardized solid for 10 minutes.
  • Example grade 1 > a punch J: requenz [lj / min] 2000 2500 3000 3200
  • Example 1 shows the result of the monofilament according to the invention, with no fibrillation at all at 2000 beats per minute, while fibrillation of less than half compared to the prior art occurs at 3200 beats.
  • Example 2 shows the result of a "dirt repellent" polyester made with fluoropolymers and the examples
  • PET / PDMS monofilaments produced according to the invention are also less stiff than known monofilaments.
  • Fig. 1 is a force / strain diagram
  • the values of the soiling indices shown in FIG. 2 show the influence of the successive cycles “soiling / washing out”. Average values of two samples after soiling and after washing are shown.
  • Curve 1 shows the monofilament thread according to the invention.
  • Curve 2 shows a comparison thread made of polyester according to the prior art, that is to say without the polydimethylsiloxane component. After (five) 5 soiling / washing cycles, the inventive monofilament indexes below 10 are achieved.
  • Figure 3 shows the result of a fibrillation test in the form of photographic images.
  • Figure 3a shows a polyester with a fluoropolymer; 3b the monofilament according to the invention. It can be seen from this that the monofilament according to the invention shows significantly low fibrillation.
  • a sample of prior art polyethylene terephthalate shows
  • the monofilament according to the invention brings an improvement in the soiling test by at least a factor of 1.5 compared to the prior art.
  • the dirt repellency of the threads modified with siloxanes shows a significant improvement compared to the standard and roughly corresponds to the fluorine-containing special threads, which are questionable due to environmental pollution.
  • the abrasion resistance of the threads is clearly increased compared to the prior art.
  • the monofilaments according to the invention are preferably suitable for use in paper machine fabrics.

Abstract

A process is disclosed for producing soil-repellent and abrasion-resistant monofilaments having 0.1 to 1.0 mm diameter from a linear PET/polydialkylsiloxane, in which the Si component with 0.15 to 2.0 % by weight Si content is incorporated into the polymer chain. The soil-repellent and abrasion-resistant monofilament has at least 36 cN/tex solidity, less than 44 % elongation in relation to the non-elongated filament, and at the same time a soiling index lower than 10 after 5 soiling cycles. This monofilament is suitable for producing screening fabrics for paper machines, fishing lines and fishing nets.

Description

Verfahren zur Herstellung von schmutzabweisenden und abrasionsbeständigen Monofilamenten und deren Verwendung Process for the production of dirt-repellent and abrasion-resistant monofilaments and their use
Die Erfindung betrifft ein Verfahren zur Herstellung von schmutzabweisenden und abrasionsbeständigen Monofilamen- ten mit einem Durchmesser von 0,1 bis 1,0 mm, aus einem linearen Polyethylenterephthalat/Polydialkylsiloxan zur Herstellung von Siebgeweben, sowie Monofilamente zu deren Verwendung.The invention relates to a process for the preparation of dirt-repellent and abrasion-resistant monofilaments with a diameter of 0.1 to 1.0 mm, from a linear polyethylene terephthalate / polydialkylsiloxane for the production of screen fabrics, and monofilaments for their use.
Unter "schmutzabweisende" Eigenschaften für Papier¬ maschinensiebe soll die Nass erschmutzung, die auch Hydrolysebeständigkeit voraussetzt, verstanden sein. Die Schmutzabweisung soll dazu dienen, die Reinigungszyklen eines Siebes zu verlängern, wobei die Reinigungsarbeit unter einem Hochdruckwasserstrahl und nötigenfalls unter Reibung mit einer Bürste vorgenommen wird. Schmutzabweisende Monofilamente werden zu technischen Geweben verarbeitet, welche im Nassteil, in der Press- sowie Trockenpartie einer Papiermaschine eingesetzt werden. Solche Siebe sind Feuchtigkeit und Temperaturen weit über 100°C, sowie beim Reinigen erhöhter mechanischer Beanspruchung ausgesetzt. Reine Polyestermonofile weisen wegen ihrer Anschmutzbarkeit, Hydrolyseanfälligkeit bzw. ihrer relativen Sprödigkeit Nachteile auf. Durch Zusatz von Additiven in Form von Stabilisatoren wurde eine Verbesserung der Hydrolysebeständigkeit erzielt. Die Erhöhung der"Soil-repellent" properties for paper machine screens are understood to mean wet soiling, which also requires resistance to hydrolysis. The dirt repellency is intended to extend the cleaning cycles of a sieve, the cleaning work being carried out under a high-pressure water jet and, if necessary, with a brush. Dirt-repellent monofilaments are processed into technical fabrics, which are used in the wet section, in the press and dryer sections of a paper machine. Such screens are exposed to moisture and temperatures well above 100 ° C, as well as to increased mechanical stress when cleaning. Pure polyester monofilaments have disadvantages because of their dirtiness, susceptibility to hydrolysis or their relative brittleness. By adding additives in the form of stabilizers, an improvement in the resistance to hydrolysis was achieved. The increase in
ERSÄΓZBLÄΓΓ (REGEL 26) schmutzabweisenden Eigenschaften wurde neben der Zugabe von Additiven auch durch geeignete Finishbehandlungen am Filament sowie Nachbehandlung am Gewebe versucht.ERSÄΓZBLÄΓΓ (RULE 26) In addition to the addition of additives, dirt-repellent properties were also tried by means of suitable finish treatments on the filament and post-treatment on the fabric.
Unter "abrasionsbeständigen" Monofilen sind solche Monofile zu verstehen, bei denen im Fibrillationstest keine in der Praxis messbare Gewichtsabnahme sowie keine oder nur geringe Fibrillationen festgestellt werden.“Abrasion-resistant” monofilaments are understood to mean those monofilaments in which no weight loss measurable in practice and no or only slight fibrillation are found in the fibrillation test.
Es wurde gefunden, dass Copolyester, welche mit Siloxanen modifiziert sind, trotz Bedenken wegen ihrer geringen Hydrolysebeständigkeit für das obengenannte Einsatzgebiet hervorragend geeignet sind, da ihre Oberflächen¬ charakteristik dank besserer Gleiteigenschaften und kleinerem Reibungskoeffizienten leicht modifiziert werden kann, wodurch die Sprödigkeit deutlich verringert und die Schmutzabweisung wesentlich verbessert wird. Zur Verbesserung der chemischen Eigenschaften wie der Hydrolysebeständigkeit können die hergestellten Flächen- gebilde leicht nachbehandelt werden.It has been found that copolyesters which are modified with siloxanes, despite concerns because of their low hydrolysis resistance, are eminently suitable for the abovementioned field of application, since their surface characteristics can be easily modified thanks to better sliding properties and a lower coefficient of friction, which significantly reduces the brittleness and the Dirt repellency is significantly improved. In order to improve the chemical properties such as the resistance to hydrolysis, the fabric can easily be post-treated.
Als besonders geeignet haben sich Polyester/ Polydimethylsiloxane erwiesen, welche entweder in Granulatform vorliegen oder durch Zugabe unmittelbar vor der Extrusion modifiziert werden. Polyoxisilane der Art, die modifizierte Polyester darstellen und als Ausgangsmaterial für den erfindungsgemässen Einsatz vorgesehen sind, sind aus der US-A-5, 123, 392 bekannt. Die bekannten chemisch modifizierten Polymere dienen zur Herstellung von hydrophilen Stapelfasern, sollen aber auch für Gewebe aus Filamentgarnen verwendet werden können. Die hydrophilen Eigenschaften ermöglichen eine rasche Aufnahme von Feuchtigkeit, und werden daher vor allem im Gemisch mit Baumwolle und Wolle eingesetzt. Garne mit den genannten hydrophilen Eigenschaften sind jedoch in der vorliegenden Form für Papiermaschinensiebe oder Angelleinen ungeeignet.Polyester / polydimethylsiloxanes, which are either in granular form or are modified by addition immediately before extrusion, have proven to be particularly suitable. Polyoxisilanes of the type which are modified polyesters and which are provided as starting material for the use according to the invention are known from US Pat. No. 5,123,392. The known chemically modified polymers are used for the production of hydrophilic staple fibers, but should also be able to be used for fabrics made from filament yarns. The hydrophilic properties enable moisture to be absorbed quickly and are therefore used primarily in a mixture with cotton and wool. However, yarns with the stated hydrophilic properties are unsuitable in the present form for paper machine screens or fishing lines.
ERSÄΓZBLÄΓT (REGEL 26) Auch aus der EP-A-0 269 023 sind silikonmodifizierte Polyester bekannt, die zur Herstellung von Fasern geeignet sind. Bei der Herstellung des Polymers werden Silikoneinheiten in einer Polyestermatrix gebildet. Diese Silikoneinheiten migrieren während der Extrusion in Luft und beim Verstrecken in die äussere Hülle des Filaments. Die erhaltene Oberfläche wirkt wie ein hydrophober Film. Die chemische Zusammensetzung im Querschnitt ist nicht homogen.ERSÄΓZBLÄΓT (RULE 26) EP-A-0 269 023 also discloses silicone-modified polyesters which are suitable for producing fibers. In the manufacture of the polymer, silicone units are formed in a polyester matrix. These silicone units migrate into air during extrusion and into the outer casing of the filament during stretching. The surface obtained acts like a hydrophobic film. The cross-sectional chemical composition is not homogeneous.
Aufgabe der Erfindung ist es, ein gleichzeitig schmutzabweisendes und abrasionsbeständiges, in seinem Querschnitt homogenen Monofilament zur Verfügung zu stellen, das den hohen Ansprüchen eines technischen Gewebes, inbezug auf seine chemischen, schmutzabweisenden, mechanischen und abrasionsbeständigen Eigenschaften genügt und besonders in der Papierindustrie Verwendung findet.The object of the invention is to provide a dirt-repellent and abrasion-resistant monofilament which is homogeneous in cross-section and which meets the high demands of a technical fabric with regard to its chemical, dirt-repellent, mechanical and abrasion-resistant properties and is used particularly in the paper industry.
Die Aufgabe wird erfindungsgemäss dadurch gelöst, dass 0,15-5,0 Gew.-% Polydialkylsiloxan durch Co-Kondensation, d.h., während der Polykondensation; in die Kette des Polymers eingebaut werden.The object is achieved according to the invention in that 0.15-5.0% by weight of polydialkylsiloxane by co-condensation, i.e. during the polycondensation; be built into the chain of the polymer.
Die Festigkeit der Monofilamente ist höher als 36 cN/tex, bei einer Dehnung von <44%, bezogen auf das ungedehnte Filament, wobei als wesentliches Merkmal in überraschender Weise eine besonders gute Schmutzabweisung und eine geringe Fibrillation auftritt. Die Schmutzabweisung ist als Anschmutzungsindex mit < 10 nach 5 Anschmutzungs/ Auswaschungszyklen, verglichen mit > 14' bei einem Polyesterfilament ohne Polydimethylsiloxan, ermittelt worden.The tenacity of the monofilaments is higher than 36 cN / tex, with an elongation of <44%, based on the unstretched filament, the key feature being surprisingly good dirt repellency and low fibrillation. The dirt repellency was determined as the soiling index with <10 after 5 soiling / washout cycles, compared to> 14 ' for a polyester filament without polydimethylsiloxane.
Es ist zweckmässig, einen Polyester zu verwenden, der aus wenigstens 85 Gew.% Polyethylenterephthalat und einem Polydialkylsiloxan besteht, wobei das Polyethylen-It is expedient to use a polyester which consists of at least 85% by weight of polyethylene terephthalate and a polydialkylsiloxane, the polyethylene
ERSAΓZBLAΠ (REGEL 26 terephthalat/ Polydialkylsiloxan im fertigen Monofilament 0,05 bis 2% Gew.-%, bevorzugt 0,1 bis 1,0 Gew.-% Silizium, bezogen auf das Polymer enthält, und die homogene Mischung zu einem Monofilament extrudiert wird. Als . besonderer Vorteil sei hervorgehoben, dass das hergestellte Monofilament über den ganzen Querschnitt eine homogene Zusammensetzung aufweist.ERSAΓZBLAΠ (RULE 26 terephthalate / polydialkylsiloxane in the finished monofilament contains 0.05 to 2% by weight, preferably 0.1 to 1.0% by weight of silicon, based on the polymer, and the homogeneous mixture is extruded into a monofilament. As . It should be emphasized that the monofilament produced has a homogeneous composition over the entire cross section.
Als Polyethylenterephthalat kommt ein solches in Frage, das eine intrinsische Viskosität von > 0.60 dl/g aufweist.A polyethylene terephthalate which has an intrinsic viscosity of> 0.60 dl / g is suitable.
Als Copolymere kommen vorzugsweise difunktionelle Polydiorganosiloxane der allgemeinen Formel:The copolymers used are preferably difunctional polydiorganosiloxanes of the general formula:
R2 R2 I I -CO-R-, [Si-0]n-Si- .,-CO- R 2 R 2 II -CO-R-, [Si-0] n -Si-., - CO-
I I R2 R2 in Frage, wobei R1 , R2 gleiche oder unterschiedliche Radikale mit 2 bis 20 Kohlenstoffatomen darstellen. Als besonders geeignet haben sich Polydimethylsiloxane (PDMS) mit R2 = CH3 erwiesen.IIR 2 R 2 in question, where R1, R2 represent the same or different radicals having 2 to 20 carbon atoms. Polydimethylsiloxanes (PDMS) with R2 = CH3 have proven to be particularly suitable.
Der Siliziumgehalt im Monofilament beträgt 0,05 bis 2,0 Gew.-%, insbesondere 0,1 bis 2% Gew.-%, bevorzugt 0,1 bis 1 ,0 Gew.-%.The silicon content in the monofilament is 0.05 to 2.0% by weight, in particular 0.1 to 2% by weight, preferably 0.1 to 1.0% by weight.
Die Verwendung der erfindungsgemässen schmutzabweisenden Monofilamente mit einem Durchmesser von 0,1 bis 1,0 mm, insbesondere von 0,2 bis 0,6 mm, ist besonders zur Herstellung von Papiermaschinensiebgeweben geeignet.The use of the dirt-repellent monofilaments according to the invention with a diameter of 0.1 to 1.0 mm, in particular 0.2 to 0.6 mm, is particularly suitable for the production of paper machine fabrics.
Die Erfindung soll anhand eines Beispiels näher beschrieben werden.The invention will be described in more detail using an example.
ERSATZBLÄΓT(REGEL26) AusfϋhrungsbeispielSPARE BLADE (RULE 26) Execution example
Die Herstellung des Polymers erfolgt in bekannter Weise durch Umesterung von Dimethylterephthalat und Ethylenglykol sowie Zugabe von 3.9 Gew.-% Polydimethylsiloxan (PDMS), und Manganacetat im gerührten Autoklaven bei 160 bis 230°C, wobei das entstehende Methanol quantitativ abdestilliert. Die anschliessende Polykondensation wird im Temperaturbereich von 245 bis 285°C unter Verwendung eines Antimonkatalysators während 200 min durchgeführt, wobei in einem ersten Schritt unter progressivem Vakuum (1000 -> 50 bar) während 40 min und in einem zweiten Schritt im Hochvakuum (<1mbar) kondensiert wird.The polymer is prepared in a known manner by transesterification of dimethyl terephthalate and ethylene glycol and addition of 3.9% by weight of polydimethylsiloxane (PDMS) and manganese acetate in a stirred autoclave at 160 to 230 ° C, the resulting methanol distilling off quantitatively. The subsequent polycondensation is carried out in the temperature range from 245 to 285 ° C using an antimony catalyst for 200 min, in a first step under progressive vacuum (1000 -> 50 bar) for 40 min and in a second step in a high vacuum (<1mbar) is condensed.
Das Polyethylenterephthalat/Polydimethylsiloxan (PET- /PDMS) wird bei einer Temperatur von 290°C geschmolzen. Die Extrusion erfolgt über eine Spinndüse mit 13 Kapillaren und einem Kapillardurchmesser von 1,8 mm mit einem Polymerdurchsatz von 486 g/min. Die extrudierten Monofilamente werden in einem Wasserbad von 70°C abgekühlt. Nach dem Abkühlen werden die Monofilamente spinnpräpariert und auf eine Restdehnung von etwa < 44% verstreckt, relaxiert und mit einer Geschwindigkeit von 100 m/min aufgewickelt. Der resultierende Faden weist einen Anschmutzungskoeffizient nach 5-fachem Behandeln von weniger als 10 (< 10) auf, hat bei einer Verstreckung von 500% eine Festigkeit (Ft) von 36,1 cN/tex bei einer Dehnung (Dt) von 38.8 %, bezogen auf das ungedehnte Monofilament.The polyethylene terephthalate / polydimethylsiloxane (PET / PDMS) is melted at a temperature of 290 ° C. The extrusion takes place via a spinneret with 13 capillaries and a capillary diameter of 1.8 mm with a polymer throughput of 486 g / min. The extruded monofilaments are cooled in a water bath at 70 ° C. After cooling, the monofilaments are spin-prepared and stretched to a residual elongation of approximately <44%, relaxed and wound up at a speed of 100 m / min. The resulting thread has a soiling coefficient after five treatments of less than 10 (<10), has a tensile strength (Ft) of 36.1 cN / tex with an elongation (Dt) of 38.8% at a stretch of 500%, based on the unstretched monofilament.
Man kann aber auch anstelle des PET/PDMS als Polymer von reinem handelsüblichen Polyester (Polyethylen-terephtha- lat) ausgehen und vor dem Extruder Polydimethylsiloxan (PDMS) mittels einer Dosiereinrichtung zufügen.Instead of PET / PDMS as a polymer, however, it is also possible to start from pure commercial polyester (polyethylene terephthalate) and to add polydimethylsiloxane (PDMS) upstream of the extruder by means of a metering device.
ERSATZBLÄΠ(REGEL26) Zur Bestimmung der schmutzabweisenden Wirkung von Monofilamenten für Papiermaschinensiebgewebe wurde folgende Methode entwickelt:REPLACEMENT BLUE (RULE 26) The following method was developed to determine the dirt-repellent effect of monofilaments for paper machine fabrics:
Prinzip der Testmethode (Anschmutzungstest)Principle of the test method (soiling test)
Es werden rostfreie Stahlplattchen dreilagig mit dem Monofil präzis bewickelt. Nach Auswaschen der Spinnpräparation und farbmetrischer Ausmessung wird die Oberseite der Probe nach einem festgelegten Verfahren achtmal unter nassem Zeitungspapier in einer Bügelpresse bei 130°C mittels "Transferdruck" angeschmutzt. Nach farbmetrischer Ausmessung wird auf eine spezifizierte Weise gewaschen, getrocknet und wieder farbmetrisch vermessen. Dieser Anschmutzungs-/Auswasch-Prozess wird für die gleichzeitige Ermittlung der "Soil-release"- Eigenschaften insgesamt fünfmal nacheinander durchgeführt. Als quantitatives Resultat werden in jedem Stadium die DL* (D65)- Werte angegeben, welche jeweils auf die Kartellen vor der ersten Anschmutzung als Referenz bezögen sind. DL* (D65) entspricht der Helligkeitsdifferenz der Probe zur Referenz bei Tageslicht. Um Einflüsse der Farbdifferenzen der Proben auszuschliessen, wird die prozentuale Helligkeitsabnahme angegeben, welche definiert ist alsThree-layer stainless steel plates are precisely wound with the monofilament. After washing out the spinning preparation and colorimetric measurement, the top of the sample is soiled eight times under wet newspaper in an ironing press at 130 ° C. using "transfer printing". After colorimetric measurement, washing, drying and measuring again are carried out in a specified manner. This soiling / washing-out process is carried out a total of five times in succession for the simultaneous determination of the “soil-release” properties. As a quantitative result, the DL * (D65) values are given at each stage, which refer to the cartels before the first soiling as a reference. DL * (D65) corresponds to the difference in brightness of the sample for reference in daylight. In order to exclude influences of the color differences of the samples, the percentage decrease in brightness, which is defined as
AI = - [DL*] / L*0 x 100AI = - [DL *] / L * 0 x 100
und Anschmutzungsindex genannt wird.and soiling index is called.
Prinzip der Testmethode (Fibrillationstest)Principle of the test method (fibrillation test)
Zur Bestimmung der Fibrillation von Monofilamenten für Papiermaschinensiebgewebe wird ein Bündel von gleichen Monofilamenten mit einer Frequenz von 2000 bis 3200 U/minTo determine the fibrillation of monofilaments for paper machine fabrics, a bundle of the same monofilaments with a frequency of 2000 to 3200 U / min
ERSÄΓZBLAΓT (REGEL 26) während 10 Minuten gegen einen genormten Festkörper geschlagen.ERSÄΓZBLAΓT (RULE 26) struck against a standardized solid for 10 minutes.
Im folgenden sind die Resultate des Fibrillationstests zusammengefasst, wobei die Benotung folgende Bedeutung hat:The results of the fibrillation test are summarized below, with the following meaning:
Benotung der FibrillationGrading of fibrillation
0.0 - 0.5 : gar keine bzw. sehr schwache Fibrillation0.0 - 0.5: no or very weak fibrillation
0.5 - 1.5 : schwache Fibrillation0.5 - 1.5: weak fibrillation
1.5 - 3.5 : mittelstarke bis starke Fibrillation1.5 - 3.5: medium to strong fibrillation
3.5 - 4.5 : sehr starke Fibrillation3.5 - 4.5: very strong fibrillation
> 4.5 : sehr starke Beschädigung> 4.5: very severe damage
Die Fibrillationstestresultate sind in der folgenden Tabelle zusammengefasst.The fibrillation test results are summarized in the following table.
Tabelletable
Beispiel Note 1 :>ei SchlagJ :requenz [lj/min] 2000 2500 3000 3200Example grade 1:> a punch J: requenz [lj / min] 2000 2500 3000 3200
1 0.0 0.1 0.5 2.51 0.0 0.1 0.5 2.5
2 0.5 1.0 0.9 4.52 0.5 1.0 0.9 4.5
3 0.4 1.1 1.5 5.03 0.4 1.1 1.5 5.0
4 0.2 0.8 1.0 5.04 0.2 0.8 1.0 5.0
Beispiel 1 zeigt das Ergebnis des erfindungsgemässen Monofilaments, wobei bei 2000 Schlägen pro Minute überhaupt keine Fibrillation auftritt, während bei 3200 Schlägen eine Fibrillation von weniger als die Hälfte gegenüber dem Stand der Technik auftritt. Beispiel 2 zeigt das Ergebnis eines mit Fluoropolymeren "schmutzabweisend" gemachten Polyesters und die BeispieleExample 1 shows the result of the monofilament according to the invention, with no fibrillation at all at 2000 beats per minute, while fibrillation of less than half compared to the prior art occurs at 3200 beats. Example 2 shows the result of a "dirt repellent" polyester made with fluoropolymers and the examples
ERSÄΓZBLAΓT (REGEL 26) 3 und 4 Standardpolyester. Die Erfindung wird anhand von Zeichnungen näher beschrieben.ERSÄΓZBLAΓT (RULE 26) 3 and 4 standard polyester. The invention is described in more detail with reference to drawings.
Die erfindungsgemäss hergestellten Monofilamente aus PET/PDMS sind ausserdem weniger steif als bekannte Monofilamente.The PET / PDMS monofilaments produced according to the invention are also less stiff than known monofilaments.
Es zeigen:Show it:
Fig. 1 ein Kraft/DehnungsdiagrammFig. 1 is a force / strain diagram
Fig. 2 Verschmutzungstestergebnisse Fig. 3 Ergebnisse des FibrillationstestsFig. 2 Pollution test results. Fig. 3 Results of the fibrillation test
Aus dem Kraft/Dehnungdiagrammen der Figur 1 geht hervor, dass die Festigkeit des erfindungsgemassen Monofilament in überraschender Weise durch die Copolymerisierung nicht abgenommen hat.1 shows that the strength of the monofilament according to the invention has surprisingly not decreased as a result of the copolymerization.
Die in der Figur 2 dargestellten Werte der Anschmutzungsindices zeigen den Einfluss der aufeinanderfolgenden Zyklen "Anschmutzen-/Auswaschen" . Es werden jeweils Mittelwerte von zwei Proben nach dem Anschmutzen und nach dem Auswaschen dargestellt. Die Kurve 1 zeigt den erfindungsgemassen Monofilamentfaden. Die Kurve 2 zeigt einen Vergleichsfaden aus Polyester nach dem Stand der Technik, also ohne die Polydimethylsiloxankomponente. Nach (fünf) 5 Anschmutz/- Auswaschzyklen werden mit dem erfindungsgemassen Monofilament Indices unter 10 erreicht.The values of the soiling indices shown in FIG. 2 show the influence of the successive cycles “soiling / washing out”. Average values of two samples after soiling and after washing are shown. Curve 1 shows the monofilament thread according to the invention. Curve 2 shows a comparison thread made of polyester according to the prior art, that is to say without the polydimethylsiloxane component. After (five) 5 soiling / washing cycles, the inventive monofilament indexes below 10 are achieved.
Figur 3 gibt das Ergebnis eines Fibrillationstests in Form von photographischen Aufnahmen wieder. Fig. 3a zeigt einen Polyester mit einem Fluorpolymer; Fig. 3b das erfindungsgemässe Monofilament. Es geht daraus hervor, dass das erfindungsgemässe Monofilament wesentlich geringe Fibrillation zeigt. Eine Probe aus Polyethylenterephthalat nach dem Stand der Technik zeigtFigure 3 shows the result of a fibrillation test in the form of photographic images. Figure 3a shows a polyester with a fluoropolymer; 3b the monofilament according to the invention. It can be seen from this that the monofilament according to the invention shows significantly low fibrillation. A sample of prior art polyethylene terephthalate shows
ERSÄΓZBLAΓT (REGEL 26) unter gleichen Bedingungen sogar eine grosse Gewichtsabnahme.ERSÄΓZBLAΓT (RULE 26) under the same conditions, even a large weight loss.
Der erfindungsgemässe Monofilfaden bringt im Anschmutzungstest eine Verbesserung um wenigstens einen Faktor 1,5 gegenüber dem Stand der Technik. Die Schmutzabweisung der mit Siloxanen modifizierten Fäden zeigt im Vergleich zum Standard eine deutliche Verbesserung und entspricht in etwa den aus Gründen der Umweltbelastung bedenklichen Fluor-haltigen Spezialfäden. Die Abrasionsbeständigkeit der Fäden ist gegenüber dem Stand der Technik eindeutig erhöht. Die erfindungsgemassen Monofilamente sind bevorzugt zum Einsatz in Papiermaschinengeweben geeignet.The monofilament according to the invention brings an improvement in the soiling test by at least a factor of 1.5 compared to the prior art. The dirt repellency of the threads modified with siloxanes shows a significant improvement compared to the standard and roughly corresponds to the fluorine-containing special threads, which are questionable due to environmental pollution. The abrasion resistance of the threads is clearly increased compared to the prior art. The monofilaments according to the invention are preferably suitable for use in paper machine fabrics.
ERSATZBLArT(REGEL26) SPARE BLART (RULE 26)

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von schmutzabweisenden und abrasionsbeständigen Monofilamenten für Siebgewebe mit einem Durchmesser von 0,1 bis 1,0 mm, aus einem linearen silikonmodifizierten Polyehylenterephthalat, dadurch gekennzeichnet, dass 0,15-5,0 Gew.-% Polydialkylsiloxan durch Co-Kondensation in die Kette des Polymers eingebaut werden.1. A process for the preparation of dirt-repellent and abrasion-resistant monofilaments for screen fabrics with a diameter of 0.1 to 1.0 mm, from a linear silicone-modified polyethylene terephthalate, characterized in that 0.15-5.0 wt .-% polydialkylsiloxane by Co- Condensation can be built into the chain of the polymer.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das silikonmodifizierte Polymer in eine wässrige Lösung extrudiert wird.2. The method according to claim 1, characterized in that the silicone-modified polymer is extruded into an aqueous solution.
3. Schmutzabweisendes und abrasionsbeständiges Mono- filament mit einem Durchmesser von 0,1 bis 1,0 mm, bestehend aus einem silikonmodifizierten Polyethylenterephthalat, dadurch gekennzeichnet, dass das Monofilament eine Festigkeit von wenigstens 36 cN/tex, eine Dehnung von < 44 %, bezogen auf das ungedehnte Filament, und gleichzeitig einen Anschmutzungsindex von < 10 nach 5 Anschmutzungs- zyklen aufweist.3. Dirt-repellent and abrasion-resistant monofilament with a diameter of 0.1 to 1.0 mm, consisting of a silicone-modified polyethylene terephthalate, characterized in that the monofilament has a strength of at least 36 cN / tex, an elongation of <44% on the unstretched filament, and at the same time has a soiling index of <10 after 5 soiling cycles.
4. Monofilament nach Anspruch 1, gekennzeichnet durch einen Si-Gehalt von 0,05 bis 2,0 Gew.-%, bezogen auf das Gewicht des Monofilaments.4. Monofilament according to claim 1, characterized by an Si content of 0.05 to 2.0 wt .-%, based on the weight of the monofilament.
5. Monofilament nach Anspruch 1, gekennzeichnet durch eine Fibrillationsnote < 0,1 bei 2000 U/min.5. Monofilament according to claim 1, characterized by a fibrillation grade <0.1 at 2000 rpm.
6. Verwendung des schmutzabweisenden und abrasions¬ beständigen Monofilaments mit einem Durchmesser von6. Use of the dirt-repellent and abrasion-resistant monofilament with a diameter of
ERSÄΓZBLAΓT (REGEL 26) 0,1 bis 1,0 mm, aus einem silikonmodifizierten Polyethyylenterephthalat mit einer Festigkeit von wenigstens 36 cN/tex, einer Dehnung von < 44 %, bezogen auf das ungedehnte Filament und gleichzeitig einen Anschmutzungsindex von < 10 nach 5 Anschmutzungszyklen, zur Herstellung von Siebgeweben für Papiermaschinen, sowie von Angelschnüren und Fischereinetzen.ERSÄΓZBLAΓT (RULE 26) 0.1 to 1.0 mm, made of a silicone-modified polyethylene terephthalate with a strength of at least 36 cN / tex, an elongation of <44%, based on the unstretched filament and at the same time a soiling index of <10 after 5 soiling cycles, for the production of sieve fabrics for paper machines, as well as fishing lines and fishing nets.
ERSAΓZBLAΓT (REGEL 26) ERSAΓZBLAΓT (RULE 26)
EP94917779A 1993-07-02 1994-06-28 Process for producing soil-repellent and abrasion-resistant monofilaments and their use Withdrawn EP0658222A1 (en)

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