WO2002077059A1 - Procede de production de materiaux de renforcement ou de revetement traites a la resine - Google Patents

Procede de production de materiaux de renforcement ou de revetement traites a la resine Download PDF

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Publication number
WO2002077059A1
WO2002077059A1 PCT/EP2002/001776 EP0201776W WO02077059A1 WO 2002077059 A1 WO2002077059 A1 WO 2002077059A1 EP 0201776 W EP0201776 W EP 0201776W WO 02077059 A1 WO02077059 A1 WO 02077059A1
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WO
WIPO (PCT)
Prior art keywords
resin
production
reinforcing
range
treated
Prior art date
Application number
PCT/EP2002/001776
Other languages
German (de)
English (en)
Inventor
Ulrich Grundke
Volker Kalla
Klaus-Peter Liebetanz
Original Assignee
Bakelite 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 Bakelite Ag filed Critical Bakelite Ag
Priority to EP02719877A priority Critical patent/EP1383818A1/fr
Publication of WO2002077059A1 publication Critical patent/WO2002077059A1/fr

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Classifications

    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08L63/10—Epoxy resins modified by unsaturated compounds

Definitions

  • the invention relates to a method for producing reinforcing or laminating materials, in particular flat structures, which are impregnated or coated with a reaction resin, the reaction resin being tack-free at room temperature but not yet cured.
  • flat structures are e.g. Prepregs or coated foils, in particular coated metal foils, which are used for the production of composite materials, in particular for the production of metal-coated or uncoated electrical laminates.
  • epoxy resins are preferred as reaction resins for these flat structures.
  • thermosetting resin According to the state of the art (cf. plastic handbook vol. 10 "Duroplast", 2nd edition (1988), p. 387 ff), flat carrier materials are impregnated or coated with thermosetting resin, dried and pre-hardened. These so-called prepregs are cut into pieces of equal size, stacked and between steel sheets or in molds pressed under heating. The resin is applied as a solution in an organic solvent, which has to evaporate after impregnation. In addition, the setting of the pre-cured state (B state) of the resin is difficult.
  • EP-A 0 142 463 discloses a process for the production of prepregs, according to which a reinforcing material is impregnated with a liquid mixture which contains an epoxy resin, a photopolymerizable compound, a heat-activated hardener for the epoxy resin and a photopolymerization catalyst for the photopolymerizable compound. After the impregnation, the structure is exposed and the photopolymerizable compound is polymerized. This creates an essentially tack-free prepreg, the epoxy resin groups of which can be thermally hardened at a later point in time, and which thus enables the production of composite materials from these prepregs.
  • the process works solvent-free and the B-state is specifically controlled by the photopolymerization.
  • the composite materials produced in this way have the disadvantage that the mechanical strengths, in particular the interlaminar shear strength, are not sufficient for high-quality applications.
  • a reactive resin such as e.g.
  • the object is achieved by a method according to claims 1 to 5 for the production of resin-treated reinforcing and laminating material, in particular prepregs, laminated metal foils or resin-treated rovings and strands, by the prepregs, laminated metal foils produced according to this method or resin-treated rovings and strands according to claims 6 to 8, and according to claim 9 by a process for the production of composite materials by heat curing molded parts which are produced from reinforcing and laminating material treated according to the invention with resin.
  • a resin system is used for the production of resin-treated reinforcing or laminating material, the partial ester of di- and / or polyepoxide compounds with one or more ethylenically unsaturated carboxylic acids and glycidyl acrylate and / or - contains methacrylate and curing catalysts and / or agents for photopolymerization and for curing the epoxy groups. If impregnated or coated sheetlike structures with such a resin system are irradiated with visible light or, preferably, with UV light, the ethylenically unsaturated groups polymerize.
  • the resin system changes into the thermoplastic B state in a reproducible manner and is stable in storage in this state until it is heated above the light-off temperature of the curing reaction of the epoxy groups.
  • This light-off temperature can be varied within a wide temperature range by selecting certain curing catalysts. Above this light-off temperature, the epoxy groups harden and the resin system becomes infusible. If flat structures produced with this resin system are pressed together above this light-off temperature, they combine to form composite materials with good electrical properties, high mechanical strengths and good chemical resistance.
  • Partial esters of di- and / or polyepoxide compounds with one or more ethylenically unsaturated carboxylic acids are reaction products known per se
  • Epoxy compounds with at least two epoxy groups in the molecule with one or more ethylenically unsaturated acid Epoxy compounds with at least two epoxy groups in the molecule with one or more ethylenically unsaturated acid.
  • acids examples include acrylic, methacrylic, cinnamon or furfurylacrylic acid.
  • the quantitative ratio of epoxy groups to ethylenically unsaturated acid is selected such that the partial ester formed generally contains at least one epoxy and one ethylenically unsaturated group in the molecule.
  • diepoxide compounds are reacted with 40 to 50% of the amount of ethylenically unsaturated acid equivalent to the epoxy groups.
  • the molar ratio of epoxy groups to ethylenically unsaturated acid is in the range from 2: 0.5 to 2: 1.5.
  • All epoxy compounds with at least two epoxy groups in the molecule can be used as the epoxy resin component for this reaction, both polyglycidyl ether and polyglycidyl ester of aliphatic and aromatic polycarboxylic acids.
  • Such epoxy resins have an epoxy equivalent of 160 -> 700.
  • Monomeric aromatic or aliphatic di- and triepoxide compounds are also preferred.
  • Examples are butanediene, dimethylpentadiene, limonene, divinylbenzene or vinylcyclohexene dioxide, diglycidyl ether and diglycidyl ether of aliphatic, araliphatic, cycloaliphatic or aromatic diols or amines, in particular diglycidyl ether of ethylene glycol, diethylene glycol, diolsole, diolsole, diolsole or diolsole, the diandiole diol, the propane Aniline and triglycidyl ether of glycerol or trimethylol propane.
  • glycidyl acrylate and / or methacrylate are mixed into the partial esters of di- and / or polyepoxide compounds.
  • the preferred amount is in the range of 5-20% by weight of glycidyl acrylate and / or methacrylate, based on the amount of the partial esters. It is surprising that the extremely reactive monomers glycidyl acrylate and methacrylate do not lead to uncontrolled reactions or to undesired high heating of the polymerizing resin mixtures either during photopolymerization or during thermal curing of the epoxy groups.
  • the reinforcing or laminating material to be treated are either woven or non-woven flat fiber material or unidirectional, endless or cut fibers or strands and foils, in particular metal foils.
  • the fiber material can consist of natural or synthetic fibers, particularly cellulose, glass, boron, steel, silicon carbide, carbon or aromatic polyamide fibers. Glass fibers in the form of woven fabrics, random fiber fleeces, rovings or strands are preferred as the reinforcing material.
  • photopolymerization catalysts are used in the resin mixtures used according to the invention (for example from DE-A 27 06 638), both those which change into an excited state when irradiated and which form free radicals which initiate the polymerization (photoinitiators ), as well as those that transfer their excitation energy obtained by irradiation directly to the ethylenically unsaturated groups and thus lead to photopolymerization (photosensitizers).
  • Photoinitiators such as, for example, benzoins, benzoin ethers, benzil dimethyl ketal, benzophenones, dithio-bis (benzothiazole), oxophosphoranes and combinations of aromatic sulfochlorides with disulfides or xanthates are preferred.
  • Photopolymerization catalysts are used in an amount of 0.5 to 10% by weight, based on the mixture of partial esters and glycidyl (meth) acrylate.
  • the resin mixture used according to the invention contains latent catalysts which do not lead to a crosslinking of the epoxy groups at room temperature, but which quickly cause curing above a light-off temperature.
  • latent catalysts which do not lead to a crosslinking of the epoxy groups at room temperature, but which quickly cause curing above a light-off temperature.
  • these are dicyandiamide, corresponding derivatives, BF 3 or BC1 3 amine complexes, acid anhydrides or their adducts, imidazoles and phenolic hardeners and metal complex catalysts.
  • Latent catalysts are particularly advantageous which act as photoinitiators both in the crosslinking of the ethylenically unsaturated groups and in the case of thermal curing as curing catalysts.
  • Examples of these are compounds of the Michler's ketone type, but in particular metal complex compounds of the general formulas I to III:
  • M is a cation of a complexing metal SR is an organic or inorganic acid residue
  • L is a chelating ligand
  • PHal is an ion of a pseudohalide
  • N is a nitrogen base x is a number in the range from 1 to 8 y is a number in the range from 1 to 5 z is a number in the range from 7 to 8 m is a number in the range from 2 to 3 n is a number in the range from 1 to 6.
  • the complexes mentioned are known as curing catalysts for curing epoxy resins, the complexes of the formulas MLxBy and M [SR] ⁇ Bz being described for the first time in WO 91/13925, and the complexes of the formula M (PHal) m (N) ⁇ from German application 198 48 329.5 are known. They are characterized by the fact that, when mixed with epoxy resins, they ensure very good storage stability at room temperature, have a low light-off temperature and the correspondingly hardened epoxy resins have good mechanical, chemical and electrical properties and a high Tg value.
  • these metal complex compounds in the resin system used according to the invention from partial esters of di- and / or polyepoxide compounds with one or more ethylenically unsaturated carboxylic acids and glycidyl acrylate and / or methacrylate also catalyze the photopolymerization of the ethylenically unsaturated groups when irradiated with UV light .
  • this polymerization reaction is restricted to the ethylenically unsaturated groups and does not lead to the curing of the epoxy groups, so that the resin system used according to the invention is in a storage-stable B state after UV radiation.
  • the epoxy groups are only cured at the desired time during the thermal treatment of the reinforcing or laminating materials treated with the resin system.
  • the metal complex compounds are used in an amount of 0.1 to 50, preferably 1 to 10,% by weight, based on the resin system.
  • the binder mixtures used according to the invention can contain further additives, such as fillers and additives, which are customary per se, in particular if they are not used in the impregnation process, but are leveled, rolled or rolled, for example in the treatment of laminating material.
  • the binder mixtures used according to the invention are used in customary impregnation processes such as dipping or spraying.
  • the viscosity of the binder mixtures used according to the invention are used in customary impregnation processes such as dipping or spraying.
  • Binder mixtures adjusted to a service viscosity in the range from to mPas. This is done without the addition of solvents simply by varying the type and composition of the individual components.
  • the process according to the invention for the production of reinforcement or lamination material treated with resin is suitable for the production of all those materials in which a reinforcement or lamination material is impregnated, impregnated or coated with a binder mixture, the binder mixture subsequently in a non-tacky, pre-hardened but still thermoplastic state ( B state) and the intermediate products (molded parts) thus produced are thermally treated with one another or with other materials, if appropriate with shaping and using pressure, the binder mixture hardening to a material which can no longer be melted and a dimensionally stable composite material thereby being formed.
  • the method is particularly suitable for the production of prepregs, for the production of laminated metal foils, in particular copper foils, and of rovings and strands treated with resin for winding and pultrusion processes.
  • Example 1 (partial esters based on bisphenol A)
  • the partial ester from Example 1 is diluted with 20% of its weight glycidyl methacrylate.
  • a resin solution is obtained with a viscosity at 25 ° C. of 750 Pas and an epoxy equivalent of 235 g / equiv.
  • This resin solution is mixed homogeneously with 1% benzil dimethyl ketal (photoinitiator) and 6% dicyandiamide (hardener).
  • Glass fabric (fabric 181 / interglass 91745) is impregnated with the impregnation mixture from example 3. After impregnation, the fabrics are exposed to UV light (360 - 400 nra) and gelled. The resulting prepregs are tack-free at room temperature. They do not harden further.
  • the partial ester from Example 2 is diluted with 35% of its weight glycidyl methacrylate.
  • a resin solution is obtained with a viscosity at 25 ° C. of 950 mPas and an epoxy equivalent of 200 g / equivalent.
  • This resin solution is mixed homogeneously with 1% benzil dimethyl ketal (photoinitiator) and 6% dicyandiamide (hardener).
  • Glass fabric (fabric 181 / interglass 91745) is impregnated with the impregnation mixture from example 5. After impregnation, the fabrics are treated with UV light (360 - 400 nm) exposed and gelled. The resulting prepregs are tack-free at room temperature. They do not harden further.
  • Example 7 prepregs; comparative example
  • An o-cresol novolak epoxy resin (Rütapox® VE 2510) is diluted with methyl ethyl ketone to a solids content of 65%.
  • This solution has a viscosity (25 ° C) of 800 mPa ' s and an epoxy equivalent of 275 g / equivalent.
  • impregnation mixture from Example 3 100 g is mixed with 50 g of talc, 50 g of silanized quartz powder and 3 g of highly disperse silica (Aerosil® 200) to form a pasty adhesive.
  • This mass is applied to a copper foil with a doctor blade in a layer thickness of 50 ⁇ m.
  • the film coated in this way is exposed to UV light (360-400 nm).
  • a storage-stable laminated copper foil which is tack-free at room temperature is obtained.
  • impregnation mixture from Example 5 100 g are mixed with 50 g of talc, 50 g of silanized quartz powder and 3 g of highly disperse silica (Aerosil® 200) to form a pasty adhesive.
  • This mass is applied to a copper foil with a doctor blade in a layer thickness of 50 ⁇ m.
  • the film coated in this way is exposed to UV light (360-400 nm).
  • a storage-stable laminated copper foil which is tack-free at room temperature is obtained.
  • Example 11 laminated film; comparative example
  • Example 7 100 g impregnation mixture from Example 7 (o-cresol novolak epoxy resin (Rütapox® VE 2510) diluted with methyl ethyl ketone to a solids content of 65% and mixed with 5% dicyandiamide) is mixed with 50 g talc, 50 g silanized quartz powder and 3 g highly disperse silica (Aerosil® 200) mixed to form a pasty adhesive. This mass is applied to a copper foil with a doctor blade, so that a dry layer thickness of 50 ⁇ m results. The film coated in this way is dried at 80 ° C. for 30 minutes.
  • Example 12 Adhesive Strengths
  • the laminated copper foils from Examples 9, 10 and 11 are pressed with a laminate of epoxy resin-impregnated prepregs (FR4 base material) at 170 ° C. for 60 minutes.
  • the adhesive strength in the roller peeling test and the glass transition temperature (T g ) are then determined. The values obtained can be found in Table 2:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de production de matériaux de renforcement ou de revêtement traités à la résine. Ce procédé consiste à imprégner ou à enduire lesdits matériaux de renforcement ou de revêtement avec un mélange de liants, renfermant des groupes epoxydes et des groupes éthyléniquement insaturés. Ces liants contiennent des esters partiels de liaisons di- et/ou polyepoxydes, renfermant un ou plusieurs acides carboxyliques éthyléniquement insaturés, de l'acrylate de glycidyle et/ou du méthacrylate de glycidyle ainsi que des catalyseurs de durcissement et/ou des moyens de durcissement pour la photopolymérisation et le durcissement des groupes epoxydes.
PCT/EP2002/001776 2001-03-22 2002-02-20 Procede de production de materiaux de renforcement ou de revetement traites a la resine WO2002077059A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02719877A EP1383818A1 (fr) 2001-03-22 2002-02-20 Procede de production de materiaux de renforcement ou de revetement traites a la resine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10113940.3 2001-03-22
DE2001113940 DE10113940A1 (de) 2001-03-22 2001-03-22 Verfahren zur Herstellung von mit Harz behandelten Verstärkungs- oder Kaschiermaterialien

Publications (1)

Publication Number Publication Date
WO2002077059A1 true WO2002077059A1 (fr) 2002-10-03

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Application Number Title Priority Date Filing Date
PCT/EP2002/001776 WO2002077059A1 (fr) 2001-03-22 2002-02-20 Procede de production de materiaux de renforcement ou de revetement traites a la resine

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EP (1) EP1383818A1 (fr)
DE (1) DE10113940A1 (fr)
TW (1) TW593462B (fr)
WO (1) WO2002077059A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011073111A1 (fr) * 2009-12-14 2011-06-23 Gurit (Uk) Ltd Pré-imprégnés dans la fabrication de matériaux composites
WO2011073107A1 (fr) * 2009-12-14 2011-06-23 Gurit (Uk) Ltd Réparation de matériaux composites

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2341613A1 (fr) * 1976-02-19 1977-09-16 Ciba Geigy Ag Fabrication de produits preimpregnes comprenant une matiere fibreuse de renforcement et une resine epoxyde
US4359370A (en) * 1980-11-24 1982-11-16 Shell Oil Company Curable epoxy-vinyl ester compositions
WO1991013925A1 (fr) * 1990-03-09 1991-09-19 Rütgerswerke Aktiengesellschaft Procede de polymerisation de composes epoxydes
EP0643103A1 (fr) * 1993-09-10 1995-03-15 Bakelite AG Liants durcissables
JPH07126350A (ja) * 1993-11-01 1995-05-16 Toshiba Chem Corp 無溶剤エポキシ樹脂組成物及びそれを用いたプリプレグ、銅張積層板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2341613A1 (fr) * 1976-02-19 1977-09-16 Ciba Geigy Ag Fabrication de produits preimpregnes comprenant une matiere fibreuse de renforcement et une resine epoxyde
US4359370A (en) * 1980-11-24 1982-11-16 Shell Oil Company Curable epoxy-vinyl ester compositions
WO1991013925A1 (fr) * 1990-03-09 1991-09-19 Rütgerswerke Aktiengesellschaft Procede de polymerisation de composes epoxydes
EP0643103A1 (fr) * 1993-09-10 1995-03-15 Bakelite AG Liants durcissables
JPH07126350A (ja) * 1993-11-01 1995-05-16 Toshiba Chem Corp 無溶剤エポキシ樹脂組成物及びそれを用いたプリプレグ、銅張積層板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 08 29 September 1995 (1995-09-29) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011073111A1 (fr) * 2009-12-14 2011-06-23 Gurit (Uk) Ltd Pré-imprégnés dans la fabrication de matériaux composites
WO2011073107A1 (fr) * 2009-12-14 2011-06-23 Gurit (Uk) Ltd Réparation de matériaux composites
CN102712772A (zh) * 2009-12-14 2012-10-03 古瑞特（英国）有限公司 用于制造复合材料的预浸料
US20120261060A1 (en) * 2009-12-14 2012-10-18 Gurit (Uk) Ltd. Prepregs for manufacturing composite materials
US9381707B2 (en) 2009-12-14 2016-07-05 Gurit (Uk) Ltd. Repair of composite materials
US10538638B2 (en) 2009-12-14 2020-01-21 Gurit (Uk) Ltd. Prepregs for manufacturing composite materials

Also Published As

Publication number Publication date
TW593462B (en) 2004-06-21
DE10113940A1 (de) 2002-09-26
EP1383818A1 (fr) 2004-01-28

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