EP0431088A1 - Procede pour fabriquer un preimpregne s'utilisant comme pli d'armature et emploi de celui-ci - Google Patents

Procede pour fabriquer un preimpregne s'utilisant comme pli d'armature et emploi de celui-ci

Info

Publication number
EP0431088A1
EP0431088A1 EP90906781A EP90906781A EP0431088A1 EP 0431088 A1 EP0431088 A1 EP 0431088A1 EP 90906781 A EP90906781 A EP 90906781A EP 90906781 A EP90906781 A EP 90906781A EP 0431088 A1 EP0431088 A1 EP 0431088A1
Authority
EP
European Patent Office
Prior art keywords
prepreg
mold
synthetic resin
resin mixture
epoxy resin
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Withdrawn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
EP90906781A
Other languages
German (de)
English (en)
Inventor
Walter Eichberger
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.)
Isovolta AG
Original Assignee
Isovolta Osterreichische Isolierstoffwerke AG
Isovolta 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 Isovolta Osterreichische Isolierstoffwerke AG, Isovolta AG filed Critical Isovolta Osterreichische Isolierstoffwerke AG
Publication of EP0431088A1 publication Critical patent/EP0431088A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3484—Stopping the foaming reaction until the material is heated or re-heated
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63C—SKATES; SKIS; ROLLER SKATES; DESIGN OR LAYOUT OF COURTS, RINKS OR THE LIKE
    • A63C5/00—Skis or snowboards
    • A63C5/12—Making thereof; Selection of particular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1228—Joining preformed parts by the expanding material
    • B29C44/1242—Joining preformed parts by the expanding material the preformed parts being concentric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1285—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements the preformed part being foamed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/001—Shaping in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/14—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements the preformed part being a lining

Definitions

  • the invention relates to a method for producing a prepreg intended as a reinforcing insert, consisting of a fabric or scrim made of high-strength reinforcing fibers as the carrier material, which is impregnated with an optionally solvent-containing, curable synthetic resin mixture.
  • the invention further relates to an advantageous use of the prepreg according to the invention in the production of a body by curing in a mold.
  • a known semi-finished product of this type is e.g. a glass fiber fabric impregnated with an epoxy resin hardener mixture, commonly referred to as a "prepreg".
  • prepregs are e.g. used for the production of tennis rackets. Blanks from these prepregs are wrapped around a tube to form a layer and - together with other curable, fiber-reinforced plastic pieces used to build the racket - inserted into a mold. This wound hose runs along the ski frame and is double-guided in the grip zone. The tube is then inflated and presses its prepreg wrapping against the inner surface of the mold. The fiber-reinforced epoxy resin introduced into the mold is then cured to the tennis racket body at elevated temperature, after which the tube is vented and pulled out of the tennis racket body.
  • the invention is first of all based on the object of specifying a prepreg as a reinforcing insert made of a fabric or scrim made of high-strength reinforcing fibers as the carrier material, which is impregnated with a synthetic resin mixture which may be present as a solution, which is used in the production of objects which are used manufactures in a mold at elevated temperature with the purpose of achieving the best possible distribution of the material in the mold, but the reinforcing function of the prepreg is retained.
  • the synthetic resin mixture used for impregnation contains a blowing agent which can be activated at elevated temperature and in that the synthetic resin mixture on or in the carrier material during and / or after the impregnation or Coating is heated without foaming the synthetic resin mixture by activating the blowing agent.
  • heating advantageously takes place to temperatures which are lower than the temperatures at which the half-life of the blowing agent is 0.1 h.
  • said heating takes place at temperatures which are lower than the temperature at which the half-life is 0.5 h.
  • a synthetic resin mixture which consists at least for the most part of an epoxy resin and a latent hardener.
  • the epoxy resin can advantageously at least for the most part consist of an epoxy resin based on Bisphenol-A-diglycidyl ether with an epoxy equivalent between 175 and 400 or the epoxy-hardener mixture can advantageously contain an amine hardener.
  • the method according to the invention is characterized in that the epoxy resin-hardener mixture contains a hardener based on dicyandiamide and optionally an accelerator or that it contains a hardener based on aromatic amines and an accelerator, if appropriate Contains boron trifluoride-A i nkomplex.
  • a glass fiber fabric or scrim with a surface weight between 150 to 1000 g / m z , preferably between 200 to 800 g / m z , or a laid and needled fiber mat, in particular a glass fiber mat, is used as the carrier material used.
  • At least the major part of the solvent contained in the synthetic resin mixture is driven off by the said heating and / or it initially lowers the viscosity of the synthetic resin mixture and, if necessary, to facilitate impregnation then, after impregnation and / or coating, the viscosity of the synthetic resin mixture is increased by a preliminary reaction.
  • the invention is also based on the object of specifying an advantageous use of the prepregs produced by the method according to the invention in the production of a body by curing in a mold.
  • the invention is characterized in that when a body is produced by curing in a mold, the mechanically load-bearing surface layers and a hollow interior Rough or has a core of lower specific weight than these mechanically supporting surface layers, that the prepreg is attached within the mold between a temporary core or permanent core which creates the later cavity and the inner surface - at least over part of the inner surface of the mold is that the materials introduced into the mold are heated thereon, so that the prepreg material foams only to 1.1 - 5 times, but preferably to 1.2 - 3 times its original volume and thereby the between Fills the core and the free space still remaining in the mold surface and that the synthetic resin mixture of the prepreg finally hardens.
  • a non-foamable cover layer or layer is applied between the prepreg layers and the inner surface of the mold, against which the semi-finished material foams and presses it against the inner surface of the mold, after which the foamed prepreg material during of curing with the cover layer or layer.
  • the prepreg material foams onto the permanent core and bonds to it during curing.
  • Fi 9- 1 shows a foamable prepreg for a charak ⁇ teristic preparation phase a schematic partial section of the mold used, and a cross-section of the ski to be produced Tennis äger framework for the manufacture of a tennis racket frame using.
  • foamable prepreg shows a schematic cross section through the mold used in the process or the arrangement of the materials introduced into the mold.
  • Fig. 3 for the manufacture of a ski, in which a foamable prepreg is used, the ski structure within a press mold is shown schematically in cross section.
  • an epoxy resin mixture is used, which consists of an epoxy resin with a latent hardener, as is usually used for the production of prepregs for curing temperatures between about 130 and 160 ° C.
  • the epoxy resin used is one based on bisphenol A diglycidyl ether with an epoxy equivalent of 230, with a hardener based on dicyandiamide and an accelerator.
  • Hardeners based on aromatic amines with an accelerator such as boron trifluoride-amine complex can also be used.
  • a glass fiber fabric in sheet form with a basis weight of 290 g / m 2 is now ⁇ impregnation solution soaked and the impregnation agent applied by means of squeeze rollers. After evaporation of the acetone in a drying zone, which takes place at a temperature of 65-70 ° C for about 8 minutes, a dry or slightly sticky prepreg with a resin content of about 40% is obtained, which is coated with a release paper is rolled up as an intermediate layer.
  • a blowing agent-free prepreg is used, which - analogously as described above - was produced by impregnating a glass fiber fabric with a now but blowing agent-free epoxy resin hardener mixture.
  • a blowing agent-free prepreg is used, which - analogously as described above - was produced by impregnating a glass fiber fabric with a now but blowing agent-free epoxy resin hardener mixture.
  • blanks made of the propellant-free prepreg and blanks made of the propellant-containing prepreg or other fiber-reinforced, hardenable plastic pieces provided for the construction of the tennis racket are placed on or on top of one another.
  • This scrim is then wrapped around a tube, so that the propellant-free prepregs come to lie on the outside, and then - as already mentioned at the beginning of the description - the whole is introduced into a heated mold and the mate introduced into the mold rialien brought to a temperature of about 140 ° C.
  • the blowing agent is activated and foams.
  • a prepreg is used which is produced on the basis of a solvent-free epoxy resin mixture, as is usually already used today for producing prepregs in which the fibrous carrier material is elongated parallel fiber rovings arranged on a surface is formed.
  • this epoxy resin mixture which consists of an epoxy resin and a latent hardener, has a viscosity of approx. 15,000 mPa.s at room temperature and can be cured well at temperatures between approx.
  • the epoxy resin mixture containing blowing agent produced in this way is shaped at a temperature of 60 ° C., at which its viscosity is now approximately 700 mPa.s, by means of a heatable doctor blade device a film of a thickness of 0.25 mm evenly applied to a continuously supplied tape-shaped release film.
  • a heatable doctor blade device a film of a thickness of 0.25 mm evenly applied to a continuously supplied tape-shaped release film.
  • glass fiber rovings drawn off from a creel are placed in parallel next to each other in the resin film.
  • the weight per unit area of these parallel rovings is 360 g / m 2 .
  • the whole is then brought or maintained at temperatures between 65-70 ° C.
  • a UD prepreg which contains no blowing agent and which - like the blowing agent-containing UD prepreg - is produced using the blowing agent-free epoxy resin mixture .
  • the tennis racket frame is then produced in the same way as described with reference to FIG. 1.
  • FIG. 2 shows the mold with the mold halves 10 and 11 used in this method and the arrangement of the materials introduced into the mold.
  • propellant-free epoxy resin fiberglass prepregs are first - with the upper mold half 11 raised - propellant-free in the lower mold half 10 to form a Layer 12 used, which protrudes over the edge of the mold inner surface of the lower mold half 10 at 13 brim.
  • a lightweight core 14 made of polyurethane foam which - somewhat reduced - already has approximately the final spatial shape of the surfboard to be produced, with blowing agent-containing epoxy resin glass fiber prepregs, as they were also used in Example 1, to form a foamable layer wound and the core 14 thus wound is inserted onto the layer 12 in the lower half 10.
  • the same propellant-free prepregs as were used to form the layer 12 are then applied to this wound core 14 in a further layer 15, which also protrudes in the form of a pen at 13 on its edge. Then the mold is closed by placing the upper mold half 11.
  • the materials used in the mold are then heated to a temperature of 120 ° C. in the heated mold halves, the epoxy resins contained in the prepregs used flowing and the prepregs containing foaming agent foaming, the material of the layers 12 and 15 against the inner surface of the mold 16 press.
  • the material 17 of the foaming prepregs completely fills the cavities that still exist in the molding space between the core 14 and the layer 15 and thereby compensates for any slight deviations from the ideal spatial shape of the lightweight core 14 that is used described in Example 1, produces a gas quantity which would increase to approximately 6 times if the prepreg volume were to expand freely.
  • a glass fiber mat in sheet form with a basis weight of 500 g / m 2 is impregnated in an impregnating machine with the blowing agent-containing epoxy resin mixture described in Example 1.
  • a touch-dry or slightly tacky prepreg with a resin content of approx. 50% is obtained, which is rolled up with a release paper as an intermediate layer.
  • Such a prepreg can now be used in the production of surfboards, as described in Example 2, it being used instead of the epoxy resin-glass fabric prepregs containing blowing agent.
  • a customary ski manufacturing process the individual ski components are connected to one another or bonded to one another in a press mold under pressure and at elevated temperature.
  • Fig. 3 now shows, if one disregards the special components used to form the ski ends D, the ski structure incorporated in the mold.
  • an epoxy resin-glass fiber roving laminate 22 serving as an intermediate layer
  • an epoxy resin-glass fiber roving laminate 23 and a wooden core 24 stacked on top of one another.
  • Layers 25 of a propellant-containing epoxy resin prepreg, of the type also used in Example 1 are then placed over the wooden core so that they also cover the side surfaces of the wooden core 24.
  • a propellant-containing epoxy resin prepreg of the type also used in Example 1
  • a shell-shaped outer shell 26 which was formed in a separate process, is now placed over the prepreg layers 25 and the mold is closed by applying the upper mold half 19.
  • the shell-shaped outer shell used is produced in a separate manufacturing process and consists, for example, of an epoxy resin glass fabric on the inside, which is connected to a decorative, wear-resistant surface layer, such as an ABS layer, on the side that will later come to the outside.
  • the ski structure is then held in the mold under pressure at a temperature of about 125 ° C. for 20 minutes.
  • the foaming agent-containing prepreg layers 25 foam and completely fill the space between the wooden core 24 and the shell-shaped outer shell 26.
  • the pressure of the propellant, particularly on the side surfaces, creates a pressure that greatly promotes adhesion to the wood core.
  • the ski components used in the press mold are intimately connected to one another and the finished ski blank is finally joined to the press mold taken.
  • plastic composite bodies of the most varied types such as tennis rackets, surfboards, skis and the like, can be produced in a simple manner and with high quality.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

Pour fabriquer un préimprégné d'armature, un tissu ou une couche de fibres d'armature haute ténacité, notamment un tissu de fibre de verre ou une couche de fibres de verre avec un poids de base compris entre 150 et 100 g/m2, de préférence entre 200 et 800 g/m2, est imprégné d'un mélange de résine synthétique durcissable renfermant un agent parogène qui peut être activé à haute température. On chauffe ensuite le mélange de résine synthétique pour éliminer le solvant, abaisser la viscosité ou éventuellement augmenter ultérieurement la viscosité par une réaction préliminaire, et de telle manière que l'agent parogène ne mousse pas. Cela se produit notamment lorsque le mélange est chauffé à des températures inférieures à la température à laquelle la demi-vie de l'agent parogène est égale à 0,1 h. Pour fabriquer des produits plastiques stratifiés, le préimprégné est placé dans un moule, conjointement avec d'autres produits de départ; le préimprégné mousse à raison seulement de 1,1 à 5 fois, de préférence 1,2 à 3 fois son volume initial, remplissant tous les vides restant dans la cavité du moule ou pressant les couches de surface contre la surface intérieure du moule, tout en conservant néanmoins sa fonction d'armature.
EP90906781A 1989-05-18 1990-05-18 Procede pour fabriquer un preimpregne s'utilisant comme pli d'armature et emploi de celui-ci Withdrawn EP0431088A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1202/89 1989-05-18
AT1202/89A AT392646B (de) 1989-05-18 1989-05-18 Verfahren zum herstellen eines als verstaerkungseinlage bestimmten prepregs sowie verwendung dieses prepregs als verstaerkungseinlage

Publications (1)

Publication Number Publication Date
EP0431088A1 true EP0431088A1 (fr) 1991-06-12

Family

ID=3508823

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90906781A Withdrawn EP0431088A1 (fr) 1989-05-18 1990-05-18 Procede pour fabriquer un preimpregne s'utilisant comme pli d'armature et emploi de celui-ci

Country Status (4)

Country Link
EP (1) EP0431088A1 (fr)
AT (1) AT392646B (fr)
AU (1) AU5664390A (fr)
WO (1) WO1990014383A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59500479D1 (de) * 1995-02-01 1997-09-11 Blizzard Gmbh Verfahren zur Herstellung eines Skis
ES2235558B1 (es) * 2002-02-22 2006-08-01 Gamesa Desarrollos Aeronauticos, S.A. Procedimiento de fabricacion de una estructura de compuesto.

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1069625A (en) * 1962-12-04 1967-05-24 Borden Chemical Company U K Lt Improvements in or relating to the manufacture of synthetic resin articles reinforced with fibrous material
DE1504269B2 (de) * 1965-07-01 1973-03-08 Fa Carl Freudenberg, 6940 Weinheim Verfahren zur herstellung von faserverstaerkten fussbettsohlen aus schaumstoffen
DE1806290A1 (de) * 1968-10-31 1970-05-06 Basf Ag Verfahren zur Herstellung poromerer Materialien
GB1434828A (en) * 1973-11-16 1976-05-05 Ici Ltd Fire-retardant polymeric material and mixture for use as fire-retardant
GB1469039A (en) * 1974-02-13 1977-03-30 Fansteel Inc Elongate composite aritcles
DE3118631C2 (de) * 1981-05-11 1983-11-17 Fritzmeier AG, 5036 Oberentfelden Verfahren zur Herstellung von Segel- bzw. Wellenreitbrettern sowie Segel- bzw. Wellenreitbrett
DE3311734A1 (de) * 1983-03-30 1984-10-11 Franz 8011 Neukeferloh Hegele Verfahren zur herstellung eines segelbretts
DE8323297U1 (de) * 1983-08-12 1986-07-03 Fritzmeier AG, Oberentfelden Segel- bzw. Wellenreitbrett
JPS62127326A (ja) * 1985-11-26 1987-06-09 Hitachi Chem Co Ltd 積層板の製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9014383A1 *

Also Published As

Publication number Publication date
WO1990014383A1 (fr) 1990-11-29
ATA120289A (de) 1990-10-15
AU5664390A (en) 1990-12-18
AT392646B (de) 1991-05-10

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