WO2005016632A1 - Procede d'assemblage precis en poids de mats impregnes de resine ou de piles de mats impregnes de resine dans la fabrication de composants smc - Google Patents

Procede d'assemblage precis en poids de mats impregnes de resine ou de piles de mats impregnes de resine dans la fabrication de composants smc Download PDF

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Publication number
WO2005016632A1
WO2005016632A1 PCT/EP2004/008374 EP2004008374W WO2005016632A1 WO 2005016632 A1 WO2005016632 A1 WO 2005016632A1 EP 2004008374 W EP2004008374 W EP 2004008374W WO 2005016632 A1 WO2005016632 A1 WO 2005016632A1
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WO
WIPO (PCT)
Prior art keywords
mass
resin
raw material
weight
dosing
Prior art date
Application number
PCT/EP2004/008374
Other languages
German (de)
English (en)
Inventor
Uwe Habisreitinger
Bernhard Nordmann
Original Assignee
Daimlerchrysler Ag
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 Daimlerchrysler Ag filed Critical Daimlerchrysler Ag
Publication of WO2005016632A1 publication Critical patent/WO2005016632A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/54Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • B29C70/545Perforating, cutting or machining during or after moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C31/00Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
    • B29C31/04Feeding of the material to be moulded, e.g. into a mould cavity
    • B29C31/08Feeding of the material to be moulded, e.g. into a mould cavity of preforms to be moulded, e.g. tablets, fibre reinforced preforms, extruded ribbons, tubes or profiles; Manipulating means specially adapted for feeding preforms, e.g. supports conveyors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/34Feeding the material to the mould or the compression means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/18Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length in the form of a mat, e.g. sheet moulding compound [SMC]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/42Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs

Definitions

  • the invention relates to a method for producing SMC parts from fiber-containing, reactive resin mats according to the preamble of claim 1, as for example from the contribution by R. Brussels and U. Weber "SMC parts fully automatic” published in the magazine plastics , Volume 79 (1989), pages 1149-1154 - briefly cited below with [1] - emerge as known.
  • a certain amount of a mixture of reactive thermosetting synthetic resin and fibers is assumed in the production of SMC parts, which is weight-matched to the finished component.
  • the coordinated amount of raw material is obtained by cutting out cut parts of a certain size and shape from a fiber mat web (prepreg web) delivered in roll form and by folding the cut parts together into a stack of mats. Such a mat stack is inserted in the correct position in an open mold of a press.
  • the molding tool is heated to a temperature at which the reactive synthetic resin reacts chemically and sets.
  • the introduced raw material is initially only heated, as a result of which the synthetic resin becomes soft and flowable.
  • the molding tool is then closed under controlled force and speed, whereby the softened raw material flows away to the side and thereby the cavity of the molding tool Fills the tool completely.
  • the mold is kept closed for a while with a defined force, so that the synthetic resin can fully react and harden. Only then can the mold be opened and the finished SMC part removed from it.
  • the article cited at the beginning [1] refers, among other things, to a fluctuating basis weight of the resin mats.
  • the resin mat sheets could not be manufactured with sufficient accuracy and / or consistency in the basis weight even today. For this reason, special measures must be taken to ensure that the mass of resin mats introduced into the mold is always of the same size, at least within a certain tolerance, in preparation for each production step of an SMC part. The higher the quality requirements for the finished product, the less the resin mass introduced can scatter around a target value.
  • the blank parts stacked up as a raw material to form a stack of mats are all rectangular in shape and all have the same width, namely the width, in one direction transverse to the resin mat web the trimmed Harzmattenbahn itself.
  • the cut parts are produced by cross cutting the resin mat web, using a pneumatically driven high-speed knife which is moved across the resin mat web, which is supported at the point of the cut by a narrow profile. The high-speed knife presumably emerges from the underside of the resin mat sheet to be cut and into a longitudinal slot of the supporting profile.
  • the rectangular dimension of the cut parts lying in the longitudinal direction of the resin mat web is used.
  • the target weight of a blank is too low, the next blank to be inserted into the raw mass of the current SMC part is cut slightly larger than the target shape or a small waste part from an earlier correction process is added.
  • This type of correction has an adverse effect on the subsequent the molding process and the component quality.
  • this manual weighing of the raw material quantity can only approximate the target weight with a very large spread, which is hardly less than the weight spread of the resin mats themselves. For this reason, a relatively large number of rejects and quality fluctuations occur in SMC parts production with manual raw material weighing.
  • EP 461 365 B1 - briefly cited below with [2] - shows a process for the production of molded plastic parts from thermoplastic, in which a weight-matched amount of heated and softened thermoplastic is placed in an open mold of a press by closing of the molding tool, the plastic mass is extruded into the cavity of the molding tool and then the workpiece still in the molding tool is cooled and finally removed from it.
  • the special feature of the method described in [2] is the provision of the heated thermoplastic in a flat preform that is roughly matched to the shape of the cavity of the molding tool, with the molding compound distribution within the preform also being roughly adapted to the requirements of the cavity of the molding tool is.
  • a thin, wide extrudate strand of hot plastic mass is placed on the heated and reversibly driven conveyor belt of a belt scale and weighed at the same time.
  • the extrudate strand is placed on the conveyor belt in a meandering manner and with a variable mass distribution due to a slow oscillating movement of the conveyor belt in the conveying direction or counter to it and due to a specific belt speed that can deviate from the extrusion speed.
  • the plastic mass to be introduced into the cavity of the molding tool should correspond exactly to a target weight, on the one hand to ensure that the cavity is completely filled, and on the other hand that the molding tool is completely closed without being oversized To allow ridges to form.
  • this is achieved by continuously weighing the extrudate strand deposited on the belt scale. After a part of the extrudate strand still hangs on the extrusion nozzle towards the end of the formation of a preform and the entire plastic mass intended for the preform is not loaded on the balance, the extruded strand is already shortly before the target weight is reached, ie when a certain weight threshold is reached separated in a very short time. If the weight of the preform, which is now completely on the belt scale, lies within a predetermined tolerance range, it is transferred to a downstream conveyor, which in turn deposits it in the opened mold. If, on the other hand, the preform formed is too heavy or too light, it is discarded and its plastic mass is recycled.
  • the weight threshold for triggering strand separation for the next preform is also corrected accordingly, ie if the preform is too heavy, the weight threshold is changed in the direction of a lower threshold weight and vice versa.
  • this type of control of the weight of the plastic mass to be introduced into a molding tool cannot be transferred to the processing of fiber-reinforced thermosets, ie not to the portioning of resin mat blanks.
  • the object of the invention is to improve the generic method in such a way that, despite fluctuating basis weight of the resin mat web, the target weight prescribed for the resin mats to be inserted can be adhered to with great accuracy for each production cycle of an SMC part, without significantly increasing the shape of the individual cut parts change.
  • this object is achieved according to the invention by the characterizing features of claim 1.
  • the raw mass is initially made available with a more or less large mass deficit compared to the target mass, using blank parts that always have the same area; at most with the maximum basis weight of the associated resin mat web, the target weight of the raw mass can be achieved in this first process step.
  • This mass deficit is determined in each individual case by weighing prior to further processing of the raw mass in the molding tool, and then additional resin mass is individually metered in from a dosing mass, so that the desired target mass is achieved individually within a narrow tolerance range.
  • a strand of pasty resin material of the same type and / or small particles cut from resin mats of the same type can be / are distributed as metering mass on the raw material provided.
  • FIG. 1 is a schematic overall view of a process plant in a plan view
  • 3 shows a scale for weighing the resin mass to be made available from a plurality of stacked blank parts for a new workpiece, the target weight being controlled by sprinkling small chips of a similar resin mat
  • 4 shows the course of the basis weight of a resin mat web to be processed over its longitudinal extent in diagram form
  • Fig. 5 shows another scale for weighing the resin composition consisting essentially of only a single blank for a new workpiece, the target weight being controlled by extruding a similar, pasty resin composition.
  • the method on which the invention is based for the serial production of SMC parts is explained on the basis of the method scheme according to FIGS.
  • the SMC parts are produced from fiber-containing, reactive resin mass, which is provided as a preliminary product in the form of a quasi-endless resin mat web 22 wound up into a supply roll 1.
  • a protective film 26 which is only removed shortly before the resin mat is processed and rolled up to form a separate roll 2.
  • the protective film is deflected towards the winding 2 against a direction of processing of the resin mat by means of a turning bar 12 located in the vicinity of the cutting table 3.
  • the side edges of the resin mat web are unsuitable for further processing and must be cut off, which in the exemplary embodiment shown is carried out by a cutting tool 20 with a saw blade 21 driven in a rotationally oscillating manner.
  • the side waste strips 28 cut off at the edge of the web are likewise deflected into waste containers 14 via turning bars 13.
  • the usable part of the resin mat web 22 is disassembled on the cutting table 3, which is provided with a very hard, seamless glass plate. Cut parts 24 and 25 (FIGS. 2 and 3) of a defined shape and size are cut out and these are stacked to form a multilayer resin mat stack 31 of a certain number of layers and arrangement. If there are waste parts that cannot be used immediately, they are discharged into a corresponding waste container 4 and collected therein.
  • the raw material to be inserted - apart from the resin material metered in to achieve the target weight - consists in each case of only a single blank 23.
  • the cutting parts are cut mechanically and automatically by means of a programmable cutting robot 5.
  • a high-frequency rotary oscillating tool is used as the cutting tool Saw blade 21 is recommended, which - driven by an electric tool 20 with an integrated oscillation gear - performs small rotary strokes around a fixed central position.
  • the resin mat web 22 on the cutting table 3 is supported by a smooth, continuous and shock and joint-free glass plate which is harder than the cutting teeth of the saw blade.
  • the cut parts cut by the robot 5 on the table 3 are stacked to form a resin mat stack 31, the cut parts being handled and moved by a handling robot 7, which in turn is operated with a specially for this task and this substrate trained resin mat gripper 27 is equipped.
  • a handling robot 7 which in turn is operated with a specially for this task and this substrate trained resin mat gripper 27 is equipped.
  • the molding tool 18 is closed by the press until the shaping surface of the cavity comes into contact with the inserted resin mat stack and clamped in the closing direction with a defined, initially still small force.
  • the resin mass heats up and softens. Due to the closing force of the molding tool, the resin mass begins to flow and thereby completely fills the cavity of the more and more closing molding tool 18.
  • the tool is then held in the closed state for a certain time with increased force, the resin composition thermally curing. After this curing time has expired, the press 8 opens the tool, the finished SMC part generally remaining in the lower, stationary mold half.
  • a removal robot 9 provided with a removal tool 29, the SMC part can be removed from the press and stored in a cooling station 11. While the cutting and handling robots 5 and 7 prepare a new resin mat stack, the opened molding tool 18 is cleaned by two cleaning robots 10, so that it is ready to receive a new resin mat stack.
  • the reason for the fluctuations in weight per unit area of the Harzmattenbahn is its density or density, which is not constant with sufficient accuracy, whereas the thickness of the Harzmattenbahn is quite uniform in the longitudinal and transverse directions. Nevertheless, the fluctuating basis weight of the resin mat web should continue to be spoken of, which is at least correct in the result.
  • the blank part (s) 23, 24, 25 In order to be able to comply with the target weight prescribed for the resin mats to be inserted for each manufacturing cycle of an SMC part with high accuracy, despite the fluctuating basis weight of the resin mat web, the blank part (s) 23, 24, 25 always tailored according to shape and / or size so that the target weight of the raw mass is at most at maximum basis weight (f q + ⁇ f) of the associated resin mat web 22, whereas in most other cases a more or less large mass deficit compared to the target mass consists. In a first step of the process, an underweight of the raw mass is therefore not only accepted, but in most cases it is even sought.
  • Gsoii means the weight of the target mass to be processed for the SMC component.
  • the raw mass made available in the first process step in the form of the blank parts of equal area is thus on average smaller than the target mass to be aimed for by the percentage fluctuation range.
  • the mass deficit of the raw material provided is determined in each individual case by weighing on a balance 15 or 15 '.
  • the deficit determined is metered individually for each individual case from a dosing mass provided, which is individually distributed over the raw mass in such an amount that the desired mass to be aimed for is achieved within a narrow tolerance range.
  • the dosing compound is metered in as long as the cut parts provided are still on the scale, with metering according to the scale display. Accordingly, dosing compound is supplied as long as the target weight has not yet been reached.
  • small particles 30 cut from resin mats of the same type are used as the dosing composition, whereas in the embodiment according to FIG. 5 a strand 43 made of pasty resin composition of the same type is used.
  • the particles 30 used as dosing mass can advantageously be obtained from the edge strips 28 separated laterally from the resin mat web by cutting them into particles with an edge length of 2-6 cm.
  • the usability of these edge strip particles can be improved by admixing a fiber-free resin. With an edge strip width of, for example, 4 cm, square particles can easily be obtained by cross-cutting the edge strip at a distance of 4 cm. If, due to the workpiece, waste parts between the waste parts cannot be avoided, in particular when multi-layer mat stacks 31 are used as raw material, these waste parts collected in the container 4 can also be processed into particles and can be used appropriately.
  • the particles used as a dosing mass are obtained from a continuous fiber-reinforced resin mat web, they should be cut out of it parallel and transverse to the fiber course of the fibers embedded in the resin mat web. As a result, the fibers remaining in the particles are least shortened and least damaged.
  • the particles 30 are stored in a closed container 35, in which an atmosphere saturated with solvent vapor is maintained. This can e.g. this is done by providing a flat shell or channel separated from the particles and filled with solvent within the container.
  • a screw conveyor 36 To meter particles 30 out of the container 35, they are conveyed out of the container 35 by means of a screw conveyor 36 through an opening which can be closed by means of a flap 37.
  • the weighing and stacking device 6 provided in the process diagram according to FIG. 1 is enlarged in FIG. 3 and shown in perspective.
  • a weighing plate 16 is arranged inside the scale 15, on which a stepped stacking device 17 for the raw material to be provided in multiple layers is fastened.
  • a large basic blank 24 is first deposited in stages on the device, whereupon two smaller blank parts 25 are deposited in each case on the individual steps and a five-part mat stack 31 is thus formed.
  • the deficit mentioned is displayed on the balance 15.
  • the dosing process for a feed of dosing compound to compensate for the deficit can be initiated automatically.
  • a horizontally movable container 35 is attached for the feeding of dosing mass, inside which the small particles 30 are stored, which are cut from a similar resin mat web.
  • a screw conveyor 36 which can be driven in rotation and which extends towards an end face of the container.
  • the flap 37 is opened and the screw conveyor is rotated so that the particles are conveyed out of the opening and remain on the uppermost layer of the resin mat stack.
  • the ejected particles are evenly distributed on the surface of the resin mat stack.
  • the flap 37 is closed and the screw conveyor is stopped; the particles still in the trap completely fill the target weight.
  • the traversing device then returns the container 35 to the starting position, so that it is ready for a new dosing process.
  • the raw mass to be introduced into the molding tool is only provided in a single blank 23 on the weighing plate 16 'of the balance 15'.
  • a more or less large mass deficit is usually found.
  • the mass deficit is compensated for by metering in a pasty mass, which is deposited in the form of an extruded strand 43 on the blank.
  • the balance 15 'and with it the cut part are traversed at a speed corresponding to the exit speed of the extrudate strand - meandering horizontally - and thus distributed evenly on the top of the cut part.
  • the extruded, fiber-reinforced plastic material is mixed and extruded from the two components of the plastic, which are stored separately, in separate containers 42 and 42 ', respectively, in a twin-screw extruder 40. Fibers are already mixed in at least one of the two components, but preferably in both, so that the extrudate strand is also fiber-reinforced.
  • the latter is provided with a closure head 41 which cuts off the extrudate strand at the exit point, for which purpose a closure needle projecting axially into the exit opening can be provided.
  • the extruder must be able to be opened easily so that it can be cleaned of any plastic residues that have reacted within the extruder.
  • the dosing process is started automatically by the scale 15 ', namely as soon as the blank is placed on the weighing plate 16' and is also stopped automatically shortly before the target weight is reached.
  • the lead at which metering is stopped is matched to the weight of the vertical part of the extruded strand that has not yet been placed on the weighing plate.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Robotics (AREA)
  • Textile Engineering (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé de fabrication de composants SMC à partir de mats imprégnés de résine, contenant des fibres, capables de réagir, consistant à découper au moins une partie de découpe (24, 25) dans une bande de mat imprégné de résine et à se munir de celle-ci en tant que matériau brut. Le matériau brut est introduit, dans une position définie, dans un moule chauffé (18) d'une presse à mouler, formé sous forme de composant SMC par extrusion, et thermodurci. L'invention vise à obtenir précisément le poids de consigne défini pour le matériau brut introduit, pour chaque cycle de fabrication, malgré les variations du poids de surface de la bande de mat imprégné de résine. A cet effet, on emploie des parties de découpe de même surface pour la formation du matériau brut, de telle manière que le poids de consigne du matériau brut est d'abord défini pour le poids de surface maximal du mat imprégné de résine correspondant, et qu'un déficit de poids existe dans un premier temps par rapport au poids de consigne. Avant traitement ultérieur, le déficit de poids par rapport au poids de consigne est déterminé par pesée, et ce déficit est compensé à l'aide d'un matériau de dosage constitué par une barre de résine pâteuse (43) du même type et/ou de petites particules (30) découpées dans des mats imprégnés de résine du même type, réparties sur le matériau brut de telle manière que le poids de consigne est obtenu individuellement.
PCT/EP2004/008374 2003-08-05 2004-07-27 Procede d'assemblage precis en poids de mats impregnes de resine ou de piles de mats impregnes de resine dans la fabrication de composants smc WO2005016632A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10335730.0 2003-08-05
DE10335730A DE10335730B3 (de) 2003-08-05 2003-08-05 Verfahren zum gewichtsgenauen Zusammenstellen von Harzmatten oder Harzmattenstapeln für die Herstellung von SMC-Teilen

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WO2005016632A1 true WO2005016632A1 (fr) 2005-02-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0461365A1 (fr) * 1990-06-12 1991-12-18 Peter Stegmaier Procédé et appareil pour alimenter un moule de compression en matière plastique
JPH04297832A (ja) * 1991-03-27 1992-10-21 Sekisui Chem Co Ltd シート状材料などの計量方法
EP0597098A1 (fr) * 1992-05-29 1994-05-18 Tsukishima Kikai Kabushiki Kaisha Dispositif de distribution automatique destine a un materiau adhesif en feuille
JPH1044153A (ja) * 1996-07-30 1998-02-17 Kawasaki Yukou Kk Smcシート材の計量供給方法
WO2003024697A1 (fr) * 2001-09-14 2003-03-27 Daimlerchrysler Ag Procede d'assemblage de piles de preimpregnes presentant un poids precis pour produire des pieces en smc

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0461365A1 (fr) * 1990-06-12 1991-12-18 Peter Stegmaier Procédé et appareil pour alimenter un moule de compression en matière plastique
JPH04297832A (ja) * 1991-03-27 1992-10-21 Sekisui Chem Co Ltd シート状材料などの計量方法
EP0597098A1 (fr) * 1992-05-29 1994-05-18 Tsukishima Kikai Kabushiki Kaisha Dispositif de distribution automatique destine a un materiau adhesif en feuille
JPH1044153A (ja) * 1996-07-30 1998-02-17 Kawasaki Yukou Kk Smcシート材の計量供給方法
WO2003024697A1 (fr) * 2001-09-14 2003-03-27 Daimlerchrysler Ag Procede d'assemblage de piles de preimpregnes presentant un poids precis pour produire des pieces en smc

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 0171, no. 09 (P - 1497) 5 March 1993 (1993-03-05) *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 06 30 April 1998 (1998-04-30) *

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