EP0636728A1 - Verfahren zur Herstellung glas Matte aus Filament - Google Patents

Verfahren zur Herstellung glas Matte aus Filament Download PDF

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Publication number
EP0636728A1
EP0636728A1 EP94401678A EP94401678A EP0636728A1 EP 0636728 A1 EP0636728 A1 EP 0636728A1 EP 94401678 A EP94401678 A EP 94401678A EP 94401678 A EP94401678 A EP 94401678A EP 0636728 A1 EP0636728 A1 EP 0636728A1
Authority
EP
European Patent Office
Prior art keywords
binder
action
size
subjected
radiation
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
EP94401678A
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English (en)
French (fr)
Other versions
EP0636728B1 (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 date
Application filed by Vetrotex France SA filed Critical Vetrotex France SA
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 glass mats with continuous wires, at least part of said wires being coated with a mixture in the liquid state capable of reacting under actinic radiation.
  • the drying can be carried out at the level of the oven ensuring the hardening of the binder; it is then necessary to provide for a further steaming of the mats.
  • Such treatment requires additional energy consumption, involves the use of relatively heavy equipment and limits productivity.
  • the mat obtained is not homogeneous; it also does not have sufficient cohesion throughout its thickness, and in particular at the level of the lower layers.
  • the object of the invention is therefore to establish a process which does not have the above-mentioned drawbacks, this process being mainly more economical and rapid and also making it possible to obtain mats having a homogeneous and sufficient cohesion throughout their thickness. , this cohesion being important for obtaining using said mats of composites having good mechanical properties.
  • This object is achieved by a method of manufacturing a mat formed by a sheet of continuous glass wires emanating from one or more dies, according to which a multiplicity of melted glass fillets is drawn from the orifices of each die.
  • the filaments are collected in at least one wire, each wire being mechanically driven by a drawing system provided with a member ensuring the projection and distribution of said wire on a collecting surface or a conveyor in transverse movement relative to the direction of the projected threads, the filaments being coated with a non-aqueous size capable of reacting under the action of actinic radiation and the glass threads being subjected, after distribution on the conveyor, to the action of one or more actinic radiations.
  • non-aqueous size designates a size composition comprising less than 10% of water, the presence of water may be necessary in certain cases, in particular in acrylic compositions to facilitate the hydrolysis of silanes.
  • the filaments formed by drawing streams of molten glass from the orifices of one or more dies are coated using a sizing device with a non-aqueous size.
  • a nonaqueous sizing eliminates the need to resort to a parboiling of the mats and therefore makes it possible, first of all, to save energy while increasing productivity. But above all, it turns out that the use of non-aqueous size capable of reacting under actinic radiation makes it possible to obtain yarns with particularly advantageous characteristics for the formation of mats having good cohesion.
  • the sizes used can be, in particular, sizes crosslinkable under the action of ultraviolet radiation or sizes crosslinkable under the action of infrared radiation.
  • the nonaqueous sizes used are sizes capable of reacting under the action of ultraviolet radiation.
  • the rate of photoinitiators within such sizes is, moreover, preferably between 2 and 5% according to the invention. Examples of size 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 size being determined according to the physical properties of the composite that is desired later. get while the binder keeps them wires within the mast by creating bonding or bonding surfaces at the crossing or contact points of the wires.
  • the deposit of size and the deposit of binder 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 those previously mentioned for the sizing.
  • This binder can be in different forms. In particular, it may be a binder reacting under the action of infrared radiation or a binder reacting under the action of ultraviolet radiation.
  • Use is preferably made of a binder capable of reacting under infrared radiation, such as a polyester, and which is in the form of a thermoplastic or thermosetting powder making it possible to create an effective point bonding of the wires.
  • the photocrosslinkable liquid binders have the disadvantage of being generally of a fairly similar nature with the sizes used.
  • the pulverized binders then tend to be distributed along the fibers by affinity with the size deposited under die, instead of remaining in the form of droplets making it possible to create points of contact.
  • the binder pressure and the spraying parameters the liquid binder tends to concentrate in the upper layers of the mats.
  • liquid binder it is nevertheless possible to use in particular mixtures based on polyurethane acrylate and N-vinylpyrrolidone in the presence of a photoinitiator.
  • non-aqueous photocrosslinkable size allows the production of yarns with particular characteristics
  • size and non-aqueous binder according to the invention allows the production of mats having certain characteristics
  • the mat is therefore preferably calendered and / or is the subject of a needling before irradiation so as to force the points of contact between wires and remove the initial bulking.
  • the binder is in powder form
  • calendering and / or needling can take place before and / or after depositing the binder
  • calendering and needling after depositing the binder has the advantage of facilitating the distribution of the powder in the thickness of the mat.
  • calendering preferably takes place before spraying the binder if the latter is in liquid form, in order to avoid having a sticky mat adhering to the calendering roller.
  • liquid binder tends to concentrate in the upper layers of the mats, as seen above, obtaining a homogeneous mat means using a large quantity of binder so as to make it penetrate by gravity to the layers lower, which can lead to the manufacture of a semi-composite that is difficult to handle. It is therefore desirable, in the case where a photocrosslinkable liquid binder is used, to perform a needling of the mat rather than a calendering or, optionally, to choose a binder so that it is immiscible with sizing to avoid problems of distribution by affinity as seen above. Needling occurs, preferably, after spraying the binder, when the binder used is liquid, to promote the creation of contact points.
  • calendering, needling and binder deposition preferably take place before irradiation, the threads becoming elastic in the opposite case and therefore retaining their initial shape whatever the intensity of calendering or needling. and the weight of binder sprayed.
  • one or more irradiation devices may be necessary.
  • a single irradiation device is necessary for the treatment of the 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 discharged.
  • the size and the binder deposited are both crosslinkable under ultraviolet radiation, a single 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 dies followed by a first irradiation, then to a second deposit of binder at the level of the last dies before irradiation final, 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 of wires by the binder, whether this is of liquid or powder nature.
  • 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.
  • strands of molten glass are drawn from dies 10 in the form of sheets of continuous filaments 11 which are coated, using sizing devices 12, with a nonaqueous sizing capable of reacting under the action of ultraviolet radiation, then which is assembled in the form of wires 14 using an assembly device 13 which can be a comb or an assembly roller with several grooves.
  • the wires are mechanically driven by stretching wheels 15 before being projected and distributed on 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 with a binder 19 in the form of thermosetting powder, then the mat consisting of the sheet of wires coated with binder is subjected to infrared radiation within a oven with infrared ramps 20 then with ultraviolet radiation 21.
  • the mat obtained is then wound around a support 22.
  • the mats obtained according to the present invention have a homogeneous cohesion throughout their thickness and the products reinforced with these mats have a mechanical resistance equivalent to that of the products reinforced with mats produced according to the traditional process by aqueous .
  • the following examples illustrate the mechanical characteristics of polyester composites using, as reinforcements, mats 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 powder binder based on unsaturated polyester 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, at a rate of 58% by weight of glass.
  • the mean breaking stress in bending measured, for the composites obtained, under the conditions defined by the ISO R178 standard, is of the order of 340 MPa, while that obtained under the same conditions and for a substantially identical reinforcement rate, for composites using a mat manufactured according to the traditional method is of the order of 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 powder binder based on unsaturated polyester 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 under the conditions defined by ISO standard R178 .
  • the value obtained is of the order of 360 MPa for the composites reinforced using the mat according to the present invention and of the order of 360 MPa also for the composites reinforced 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 process according to the invention therefore makes it possible to obtain, quickly and economically, mats having satisfactory cohesion and homogeneity in thickness, this cohesion and this homogeneity being in particular favorable for obtaining composite products having a resistance mechanical at least as good as that of the composites obtained using the mats manufactured according to the traditional process by aqueous route.
  • the mats according to the invention are used, inter alia, to reinforce organic matrices.

Landscapes

  • 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)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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
FR9309321A FR2708635B1 (fr) 1993-07-29 1993-07-29 Procédé de fabrication de mats de verre à fils continus.
FR9309321 1993-07-29

Publications (2)

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

Family

ID=9449739

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)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984000424A1 (en) * 1982-07-19 1984-02-02 Desoto Inc Low temperature-flexible radiation-curable unsaturated polysiloxane coatings for fiber optic application
EP0114345A2 (de) * 1982-12-27 1984-08-01 Western Electric Company, Incorporated Durch Bestrahlung härtbarer Vielfaser-Verbund
EP0142463A2 (de) * 1983-08-24 1985-05-22 Ciba-Geigy Ag Verfahren zur Herstellung von Prepregs und die damit erhältlichen verstärkten Verbundstoffe
US4660927A (en) * 1982-08-18 1987-04-28 Shin-Etsu Chemical Co., Ltd. Quartz glass-made optical fibers coated with a silicone composition
EP0243275A1 (de) * 1986-04-24 1987-10-28 Vetrotex Saint-Gobain Verfahren und Vorrichtung zur Herstellung von Glasgarnen durch mechanisches Ziehen und erhaltene Gegenstände
EP0431439A2 (de) * 1989-12-05 1991-06-12 Ube-Nitto Kasei Co. Ltd. Vorrichtung und Verfahren zur Herstellung einer Glasfasermatte

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984000424A1 (en) * 1982-07-19 1984-02-02 Desoto Inc Low temperature-flexible radiation-curable unsaturated polysiloxane coatings for fiber optic application
US4660927A (en) * 1982-08-18 1987-04-28 Shin-Etsu Chemical Co., Ltd. Quartz glass-made optical fibers coated with a silicone composition
EP0114345A2 (de) * 1982-12-27 1984-08-01 Western Electric Company, Incorporated Durch Bestrahlung härtbarer Vielfaser-Verbund
EP0142463A2 (de) * 1983-08-24 1985-05-22 Ciba-Geigy Ag Verfahren zur Herstellung von Prepregs und die damit erhältlichen verstärkten Verbundstoffe
EP0243275A1 (de) * 1986-04-24 1987-10-28 Vetrotex Saint-Gobain Verfahren und Vorrichtung zur Herstellung von Glasgarnen durch mechanisches Ziehen und erhaltene Gegenstände
EP0431439A2 (de) * 1989-12-05 1991-06-12 Ube-Nitto Kasei Co. Ltd. Vorrichtung und Verfahren zur Herstellung einer Glasfasermatte

Also Published As

Publication number Publication date
EP0636728B1 (de) 1998-02-04
ES2114150T3 (es) 1998-05-16
FR2708635A1 (fr) 1995-02-10
DE69408376D1 (de) 1998-03-12
DE69408376T2 (de) 1998-07-16
FR2708635B1 (fr) 1995-10-20

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