EP0486651A1 - Preimpregne, procede de fabrication et application - Google Patents

Preimpregne, procede de fabrication et application

Info

Publication number
EP0486651A1
EP0486651A1 EP91910945A EP91910945A EP0486651A1 EP 0486651 A1 EP0486651 A1 EP 0486651A1 EP 91910945 A EP91910945 A EP 91910945A EP 91910945 A EP91910945 A EP 91910945A EP 0486651 A1 EP0486651 A1 EP 0486651A1
Authority
EP
European Patent Office
Prior art keywords
prepreg
phenolic resin
mixture
phenol
fibers
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Withdrawn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
EP91910945A
Other languages
German (de)
English (en)
Inventor
Walter Eichberger
Peter Walter
Wolfgang Wimmer
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 EP0486651A1 publication Critical patent/EP0486651A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention relates to a prepreg based on unidirectionally arranged reinforcements impregnated with durable plastics.
  • Kung fibers such as glass fibers, carbon fibers, aramid fibers and the like.
  • prepregs are produced by impregnating reinforcing fibers with 10 thermosetting plastics. These prepregs are preferably used to manufacture composite parts for aircraft and mechanical engineering and for the manufacture of sports articles. These composite parts are now subject to a number of requirements, such as high dynamic mechanical properties and high temperature and chemical resistance . It is known to use prepregs for such composite parts, the reinforcing fibers of which are impregnated with highly functional epoxy resins, whereby the desired temperature and chemical resistance may not be achieved, but the required dynamic mechanical properties such as sufficient toughness can be achieved in the finished composite parts.
  • the invention is based on the object, a prepreg based on unidirectionally arranged, with thermoset plastic
  • the prepreg according to the invention which is characterized in that its reinforcing fibers with a plastic mixture, an epoxy resin, a phenolic resin, optionally an accelerator and optionally additives such as fillers, flame retardants, elasticizers, wetting agents and the like ., are impregnated, the proportions of reinforcing fibers in the prepreg advantageously being 30-80% by weight, 70-20% by weight of epoxy-phenolic resin mixture and 0-30% by weight of additives.
  • the prepreg according to the invention contains a phenol-formaldehyde condensation product in the molar ratio of phenol to formaldehyde in the resin mixture as phenolic resin from 1: 0.5 to 1: 0.9, but advantageously from 1: 0.6 to 1: 0 , 85.
  • the invention is also based on the object of specifying a method for producing the prepreg according to the invention.
  • a solvent in the range of 0-20% by weight is added to the epoxy-phenolic resin mixture before the impregnation process, this mixture being applied by means of a doctor blade to a continuously moving film in the form of a layer, into which then the tapered, endless reinforcing fibers are pressed in and thereby impregnated.
  • a solvent-free epoxy resin-phenolic resin mixture is used for the impregnation, which is brought to an elevated temperature before the impregnation process in order to reduce the viscosity.
  • This scrim advantageously runs through impregnated Reinforcing fibers additionally a heating device in which the epoxy resin-phenolic resin mixture is converted into the B state and the solvent which may be present is evaporated, and then, if appropriate, a calender. Furthermore, a phenol-formaldehyde condensation product with a molar ratio of phenol to formaldehyde of 1: 0.5 to 1: 0.9, advantageously from 1: 0.6 to 1: 0.85, is preferably used.
  • the prepregs according to the invention are advantageously used for the production of hot-cured composite materials, the curing taking place, for example, in a closed form, but also in a state wound on a mandrel.
  • the bending strength losses of the laminate A produced from the prepreg according to the invention are compared before and after a so-called high-pressure cooker test in comparison to the corresponding measured values on comparative products B, C and D.
  • These are laminates which have been produced from prepregs which have been cured with nitrogen-containing compounds.
  • the phenol-formaldehyde condensation product required for the preparation of the prepreg is produced in two stages, the first stage being phenol and formaldehyde in an aqueous solution in a molar ratio of phenol: formaldehyde in the range from about 1: 0.3 to 1: 0 , 7 are added, an acidic medium is established by adding a volatile acid and the whole is kept at an elevated temperature until the condensation reaction has ended, so that in a second stage the reaction product of the first stage is added a small part consists of phenol and otherwise predominantly dihydroxydiphenylmethane, formaldehyde is added in an amount so that the molar ratio in the first stage Phenol used
  • the total amount of formaldehyde reacted in both stages is advantageously in the range from 1: 0.5 to 1: 0.9, advantageously 1: 0.6 to 1: 0.85, and the condensation reaction is continued at elevated temperature and ended, and that the condensation product is separated from the water and allowed to solidify outside the reaction kettle and com
  • the resulting composite is passed through a heating zone, in which a temperature of 110 ° to 160 ° C prevails, whereby the desired B state of the impregnating resin is achieved.
  • the prepreg is then passed through a calender and then cooled to room temperature in a cooling zone.
  • test specimens for the High-pressure cooker test 15 layers of the prepregs produced as described are pressed into laminates and cured under a pressure of 7 bar at 170 ° C.
  • the test specimens for the High-pressure cooker test For this purpose, the test specimens A, B, C and D are heated in an autoclave for one hour at 120 ° C./1.5 bar and then for two hours at 140 ° C./2.7 bar under steam.
  • the flexural strength (MPa) of the test specimens was determined before and after the test.
  • Hot-hardened composite materials with high permanent temperature and chemical resistance as well as composite parts for aircraft and mechanical engineering as well as for the manufacture of sporting goods are manufactured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Préimprégné à base de fibres de renforcement, comme des fibres de verre, des fibres de carbone, des fibres d'aramide et similaires, disposées dans une seule direction et imprégnées par un mélange de matières plastiques duromères, dans lequel le mélange de matières plastiques contient une résine époxyde, une résine phénolique, le cas échéant un accélérateur et le cas échéant des additifs comme des charges, des retardateurs de flamme, des élastifiants, des agents mouillants et similaires. Ce préimprégné sert de matériau de départ pour des matériaux composites pressés à chaud ainsi que pour des éléments composites à constance thermique élevée et résistance élevée aux produits chimiques.
EP91910945A 1990-06-13 1991-06-13 Preimpregne, procede de fabrication et application Withdrawn EP0486651A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1284/90 1990-06-13
AT0128490A AT396240B (de) 1990-06-13 1990-06-13 Prepreg verfahren zu seiner herstellung und seine verwendung

Publications (1)

Publication Number Publication Date
EP0486651A1 true EP0486651A1 (fr) 1992-05-27

Family

ID=3510559

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91910945A Withdrawn EP0486651A1 (fr) 1990-06-13 1991-06-13 Preimpregne, procede de fabrication et application

Country Status (5)

Country Link
EP (1) EP0486651A1 (fr)
JP (1) JPH05501283A (fr)
KR (1) KR920702385A (fr)
AT (1) AT396240B (fr)
WO (1) WO1991019755A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59204678D1 (de) * 1991-11-08 1996-01-25 Ruetgerswerke Ag Bindemittelsysteme auf Basis von Epoxydharz-Phenolharz-Kombinationen
AT404240B (de) * 1996-04-25 1998-09-25 Isovolta Laminat bestehend aus einer basis- und deckschicht sowie verfahren zur herstellung einer dekoroberfläche an diesem laminat
GB2352249B (en) * 1999-07-21 2004-04-14 Rover Group A method of manufacture of a glass fibre pre-preg for use in a polymer glazing application
JP5762294B2 (ja) * 2008-10-15 2015-08-12 スリーエム イノベイティブ プロパティズ カンパニー 一方向に整列した繊維を含む補強当て布
US20170087806A1 (en) 2014-03-28 2017-03-30 E I Du Pont De Nemours And Company Fiber-reinforced composite laminate and articles made therefrom

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB888607A (en) * 1958-06-18 1962-01-31 Acoplast Kunststoff Verarbeitu Improvements in and relating to the continuous production of profiled plastic sheets
US3784659A (en) * 1972-01-13 1974-01-08 R Lupert Method of producing continuous plastic shapes
US3898113A (en) * 1972-09-07 1975-08-05 Gen Tire & Rubber Co Method of making a continuous strand sheet molding compound
JPS6037810B2 (ja) * 1978-12-08 1985-08-28 東邦レーヨン株式会社 ストランドプリプレグ組成物
GB2086444B (en) * 1980-09-18 1985-01-23 Sumitomo Chemical Co Process for continuous production of prepreg sheets
JPS59155044A (ja) * 1983-02-23 1984-09-04 三井化学株式会社 プリプレグおよび積層体
US4501787A (en) * 1983-04-29 1985-02-26 Westinghouse Electric Corp. Flame retardant B-staged epoxy resin prepregs and laminates made therefrom
US4599268A (en) * 1984-04-16 1986-07-08 International Business Machines Corporation Product containing an epoxy composition
DE3508600A1 (de) * 1985-03-11 1986-09-11 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur herstellung von mit harz impraegnierten substraten zur verwendung bei der herstellung von laminaten fuer gedruckte schaltungen und danach hergestellte prepregs und laminate
JPH02120330A (ja) * 1988-10-28 1990-05-08 Shin Kobe Electric Mach Co Ltd 積層板の製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9119755A1 *

Also Published As

Publication number Publication date
WO1991019755A1 (fr) 1991-12-26
KR920702385A (ko) 1992-09-03
JPH05501283A (ja) 1993-03-11
AT396240B (de) 1993-07-26
ATA128490A (de) 1992-11-15

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