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EP0636728B1 - Verfahren zur Herstellung einer Glasfasermatte aus Filamenten - Google Patents

Verfahren zur Herstellung einer Glasfasermatte aus Filamenten Download PDF

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Publication number
EP0636728B1
EP0636728B1 EP19940401678 EP94401678A EP0636728B1 EP 0636728 B1 EP0636728 B1 EP 0636728B1 EP 19940401678 EP19940401678 EP 19940401678 EP 94401678 A EP94401678 A EP 94401678A EP 0636728 B1 EP0636728 B1 EP 0636728B1
Authority
EP
European Patent Office
Prior art keywords
binder
process according
radiation
under
subjected
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 - Lifetime
Application number
EP19940401678
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English (en)
French (fr)
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EP0636728A1 (de
Inventor
Patrick Moireau
Michel Droux
Fabrice Duchamp
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.)
Saint Gobain Adfors SAS
Original Assignee
Vetrotex France SA
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Publication of EP0636728A1 publication Critical patent/EP0636728A1/de
Application granted granted Critical
Publication of EP0636728B1 publication Critical patent/EP0636728B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • D04H3/004—Glass yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D04H3/105—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by needling
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding

Definitions

  • the present invention relates to a method for manufacturing mats of glass with continuous strands, at least part of said strands being coated with a mixture in the liquid state capable of reacting under actinic radiation.
  • the threads in question may be also coated with a binder capable of ensuring their cohesion within the mat after passing through an oven.
  • a binder capable of ensuring their cohesion within the mat after passing through an oven.
  • drying can be done at the level an oven ensuring the hardening of the binder; it is then necessary to plan further baking of the mats.
  • such treatment presupposes a additional energy consumption, involves the use of facilities relatively heavy and limits productivity.
  • the mat obtained is not homogeneous; it also does not exhibit cohesion sufficient throughout its thickness, and in particular at the level of the lower layers.
  • Patent application EP-A-0 243 275 describes a method for manufacturing wires glass by mechanical drawing during which a possibly aqueous mixture reacting under the action of actinic radiation is deposited on filaments of glass being drawn before gathering said filaments into at least one glass and exposure of the wire (s), still being drawn, to the action of a actinic radiation. This process however requires the use of sizing particularly reactive and therefore expensive.
  • the object of the invention is therefore to establish a process which does not have the disadvantages mentioned above, this process being mainly more economical and fast and also making it possible to obtain mats with cohesion homogeneous and sufficient throughout their thickness, this cohesion being important for obtaining using said mats of composites having good properties mechanical.
  • This object is achieved by a method of manufacturing a mat formed of a layer of continuous glass threads emanating from one or more channels, according to which draws from the orifices of each die a multiplicity of melted glass fillets in the form of sheets of continuous filaments, the filaments are coated with a size non-aqueous likely to react under the action of actinic radiation and then gathers the filaments in at least one thread, each thread being mechanically driven by a stretching system provided with a member ensuring projection and distribution of said wire on a collecting surface or a conveyor in transverse movement by relation to the direction of the projected wires, characterized in that one projects on the wires of glass a non-aqueous binder capable of reacting under the action of radiation actinic and in that the glass strands are subjected, after distribution on the conveyor, to the action of one or more actinic radiation.
  • non-aqueous size designates a sizing composition comprising less than 10% water, the presence of water which may be necessary in certain cases, in particular in compositions acrylics to facilitate the hydrolysis of silanes.
  • the filaments formed by drawing glass nets melted from the orifices of one or more dies are coated with a sizing device for a non-aqueous size.
  • a non-sizing aqueous eliminates the need to use a steaming of the mats and therefore allows, in first, to save energy while increasing productivity. But above all, it turns out that the use of sizing non-aqueous likely to react under actinic radiation allows obtaining yarns with particularly advantageous characteristics for formation of mats with good cohesion.
  • the son after contact with the surface of the drawing device, have a more flattened shape than those obtained when using sizing aqueous and, therefore, at the level of the mat, a covering capacity more important. The cohesion of the threads within the mast is thus found improved.
  • the sizes used can be, in particular, sizes crosslinkable under the action of ultraviolet radiation or sizing crosslinkable under the action of infrared radiation.
  • non-aqueous sizes used are sizes capable of reacting under the action of ultraviolet radiation.
  • the rate of photoinitiators in such sizing is, moreover, preferably between 2 and 5% depending on the invention. Examples of sizes according to the invention are given later in Examples 1 and 2.
  • the size ensures in particular the protection of the threads against abrasion, while giving them the properties essential for subsequent transformations, the choice of the size being determined according to the physical properties of the composite that we want to obtain later, while the binder keeps the threads within the mast by creating bonding or bonding surfaces at the points crossing or contacting the wires.
  • the size deposit and the binder deposit according to the invention are therefore preferably carried out in separate operations.
  • the binder is preferably deposited on the moving mat before the mat is subjected to actinic radiation.
  • the binder is also non-aqueous for the same reasons as above mentioned for sizing.
  • This binder can be in different forms. In particular, it may be a binder reacting under the action of radiation infrared or a binder reacting under the action of ultraviolet radiation.
  • a binder capable of reacting under infrared radiation is used, such as polyester, and in the form of a thermoplastic powder or thermosetting to create an effective point bonding of the wires.
  • photocrosslinkable liquid binders have the disadvantage of being generally fairly similar in nature to the sizes used.
  • Binders pulverized then tend to be distributed along the fibers by affinity with the size deposited under die, instead of remaining in the form of droplets allowing to create contact points.
  • the liquid binder has tendency to concentrate in the upper layers of the mats.
  • a binder liquid it is nevertheless possible to use in particular mixtures based on of polyurethane acrylate and N-vinylpyrrolidone in the presence of a photoinitiator.
  • size and non-aqueous binder according to the invention makes it possible to obtain mats with certain peculiarities.
  • the mat obtained is on the other hand more swelling, no longer having to undergo the weight of water from different primers (a aqueous size indeed contains at least 90% by weight of water and gives a mat with a water content of at least 20%).
  • the swelling of the mat translates by a reduced number of contact points between wires and a thickness important. Only the weight of the binder can, by gravity, force the appearance of points of contact between wires which requires the use of large quantities of binder to bind the lower layers.
  • the mat is therefore preferably calendered and / or needled before irradiation of so as to force the points of contact between the wires and remove the initial bulk.
  • calendering and / or needling can occur before and / or after depositing the binder, calendering and needling after depositing the binder having the advantage of facilitating the distribution of the powder in the thickness of the mat.
  • calendering occurs preferably before spraying the binder if it is in liquid form, in order to avoid having a mat sticky and adhering to the calendering roller.
  • liquid binder tends to to concentrate in the upper layers of the mats, as seen previously, obtaining a homogeneous mat is equivalent to using a quantity significant binder so as to make it penetrate by gravity to the layers which can lead to the production of a semi-composite difficult to handle. It is therefore desirable, in the event that a photocrosslinkable liquid binder is used, needling the mat rather than calendering or, possibly, choosing a binder so that be immiscible with the size to avoid distribution problems by affinity as seen previously. Needling takes place, preferably, after spraying the binder, when the binder used is liquid, to promote the creation of contact points.
  • the calendering, needling and deposition of binder preferably intervene before irradiation, the wires becoming otherwise elastic and therefore retaining their initial shape which whether the intensity of calendering or needling and the weight of binder sprayed.
  • one or more irradiation devices may be required. So, in case the size and the binder deposited are both crosslinkable under radiation infrared, only one irradiation device is necessary for the treatment of mats. The duration of the heating intended for the modification of the state of the binder is then very reduced due to the absence of water to be evacuated.
  • the size and the binder deposited are both crosslinkable under ultraviolet radiation, only one irradiation device is necessary.
  • the mat it is also possible to subject the mat to a first deposit of binder at the level of the first channels followed by a first irradiation, then a second deposit of binder at the level of last channels before final irradiation, each of these deposits being preceded and / or followed by calendering and / or needling according to what has been seen previously.
  • This process notably facilitates the impregnation of the layer son by the binder, whether it is liquid or powdered.
  • it requires at least two binder spraying devices and, optionally, two calendering and / or needling devices.
  • the figure shows a schematic front view of an installation allowing the implementation of the method according to the invention.
  • glass nets are drawn from dies 10 melted in the form of sheets of continuous filaments 11 which are coated, using sizing devices 12, a non-aqueous sizing capable of react under the action of ultraviolet radiation, then that we gather under form of wires 14 using an assembly device 13 which can be a comb or assembly roller with several grooves.
  • the sons are trained mechanically by stretching wheels 15 before being projected and distributed over a moving conveyor 16 transverse to the direction of the projected wires.
  • the wires are then calendered between two rollers 17, 18 before being coated of a binder 19 in the form of a thermosetting powder, then the mat consisting by the layer of wires coated with binder is subjected to infrared radiation in an oven with infrared ramps 20 and then with ultraviolet radiation 21.
  • the mat obtained is then wound around a support 22.
  • the mats obtained according to the present invention exhibit cohesion homogeneous throughout their thickness and the products reinforced with these mats have a mechanical resistance equivalent to that of the products reinforced with mats made according to the traditional process by aqueous.
  • the following examples illustrate the mechanical characteristics of the polyester composites using as reinforcements mat produced according to the invention and also give examples of sizing compositions used in the context of the invention.
  • the binder used is, moreover, a polyester-based powder binder unsaturated marketed by Cray Vallée under the reference Stratyl P 80 A3. It is added to the mat in proportions of 6% by weight of the mat.
  • Said mat is calendered before depositing the binder by means of a roller, then heated in an infrared oven at 180 ° C and subjected to the action of ultraviolet radiation.
  • the mat obtained is then used to reinforce polyester matrices, 58% by weight of glass.
  • the constraint of mean failure in measured bending, for the composites obtained, in the conditions defined by ISO standard R178, is around 340 MPa, while than that obtained under the same conditions and for a reinforcement rate substantially identical, for composites using a mat manufactured according to the traditional process is around 360 MPa, the standard deviations on the series of measurements carried out being of the order of 20 MPa.
  • the binder used is, moreover, a polyester-based powder binder unsaturated marketed by Cray Vallée under the reference Stratyl P 80 A3. It is added to the mat in proportions of 6% by weight of the mat.
  • the mat is prepared in the same way as in Example 1 and the mean breaking stress in bending for a reinforcement rate of the order of 54% is also measured for polyester composites in conditions defined by ISO R178.
  • the value obtained is of the order of 360 MPa for composites reinforced with the mat according to this invention and around 360 MPa also for reinforced composites using the mat manufactured according to the traditional process, the standard deviations on the series of measurements carried out being of the order of 20 MPa.
  • the method according to the invention therefore makes it possible to obtain, quickly and economical, mats with cohesion and homogeneity satisfactory in thickness, this cohesion and this homogeneity being particularly favorable for obtaining composite products having a mechanical strength at least as good as that of the composites obtained at using masts made according to the traditional process by aqueous route.
  • the masts according to the invention are used, inter alia, to reinforce organic matrices.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (8)

  1. Verfahren zur Herstellung einer Matte aus einem Vlies von Endlosglasfäden aus einer oder mehreren Düsen, bei welchem man aus den Öffnungen einer jeden Düse eine Vielzahl von dünnen Fäden aus Glasschmelze in Form von Bündeln von endlosen Elementarfäden zieht, die Elementarfäden mit einer nicht-wässrigen Schlichte beschichtet, die unter Einwirkung einer aktinischen Strahlung reagiert, dann die Elementarfäden zu mindestens einem Faden zuzammenführt, wobei jeder Faden mechanisch durch eine Zieheinrichtung mitgenommen wird, die mit einer Einrichtung ausgestattet ist, welche die Aufgabe und die Verteilung des Fadens auf einer Sammelfläche oder einen Förderer in Querbewegung bezüglich der Richtung der abgeworfenen Fäden sicherstellt, dadurch gekennzeichnet, daß auf die Glasfäden ein nichtwässriges Bindemittel aufsprüht wird, das unter der Einwirkung einer aktinischen Strahlung reagiert, und daß die Glasfäden nach Verteilung auf dem Förderer der Einwirkung von einer oder mehreren aktinischen Strahlungen ausgesetzt werden.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die benutzte Schlichte eine unter der Einwirkung einer ultravioletten Strahlung vernetzbare Schlichte ist und daß die Glasfäden mindestens einer ultravioletten Strahlung unterworfen werden.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die benutzte Schlichte eine unter der Einwirkung einer infraroten Strahlung vernetzbare Schlichte ist und daß die Glasfäden mindestens einer infraroten Strahlung unterworfen werden.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das benutzte Bindemittel ein unter der Einwirkung einer ultravioletten Strahlung vernetzbares Bindemittel ist und daß die Glasfäden mindestens einer ultravioletten Strahlung unterworfen werden.
  5. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das benutzte Bindemittel ein unter der Einwirkung einer infraroten Strahlung vernetzbares Bindemittel ist und daß die Glasfäden mindestens einer infraroten Strahlung unterworfen werden.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Bindemittel in Form von Pulver aus thermoplastischem oder wärmehärtenden Polymeren verwendet wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Glasfäden einem erstem Bindemittelauftragung und einer ersten Bestrahlung auf dem Niveau der ersten Düsen und dann einer zweiten Bindemittelauftragung und einer zweiten Bestrahlung auf ihrer Gesamtheit beim Verlassen aus den letzten Düsen unterworfen werden.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß jede Bindemittelauftragung einem Kalandrieren und/oder einem Nadeln vor der aktinischen Bestrahlung vorhergeht und/oder folgt.
EP19940401678 1993-07-29 1994-07-21 Verfahren zur Herstellung einer Glasfasermatte aus Filamenten Expired - Lifetime EP0636728B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9309321 1993-07-29
FR9309321A FR2708635B1 (fr) 1993-07-29 1993-07-29 Procédé de fabrication de mats de verre à fils continus.

Publications (2)

Publication Number Publication Date
EP0636728A1 EP0636728A1 (de) 1995-02-01
EP0636728B1 true EP0636728B1 (de) 1998-02-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19940401678 Expired - Lifetime EP0636728B1 (de) 1993-07-29 1994-07-21 Verfahren zur Herstellung einer Glasfasermatte aus Filamenten

Country Status (4)

Country Link
EP (1) EP0636728B1 (de)
DE (1) DE69408376T2 (de)
ES (1) ES2114150T3 (de)
FR (1) FR2708635B1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496210A (en) * 1982-07-19 1985-01-29 Desoto, Inc. Low temperature-flexible radiation-curable unsaturated polysiloxane coated fiber optic
JPS5935044A (ja) * 1982-08-18 1984-02-25 Shin Etsu Chem Co Ltd 光通信フアイバ−用被覆剤
US4479984A (en) * 1982-12-27 1984-10-30 At&T Bell Laboratories Radiation curable multifilament composite
DE3479810D1 (en) * 1983-08-24 1989-10-26 Ciba Geigy Ag Method of producing prepregs and composite materials reinforced therewith
FR2597856B1 (fr) * 1986-04-24 1992-01-10 Saint Gobain Vetrotex Procede de traitement de fibres de verre continues et produits en resultant
US5129131A (en) * 1989-12-05 1992-07-14 Ube-Nitto Kasei Co., Ltd. Method of and apparatus for manufacturing glass fiber mat

Also Published As

Publication number Publication date
EP0636728A1 (de) 1995-02-01
DE69408376T2 (de) 1998-07-16
FR2708635A1 (fr) 1995-02-10
ES2114150T3 (es) 1998-05-16
FR2708635B1 (fr) 1995-10-20
DE69408376D1 (de) 1998-03-12

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