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WO1984000554A1 - Matiere moulable contenant un produit fibreux sous la forme de microfibres en deux ou en trois dimensions - Google Patents

Matiere moulable contenant un produit fibreux sous la forme de microfibres en deux ou en trois dimensions Download PDF

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Publication number
WO1984000554A1
WO1984000554A1 PCT/DE1983/000135 DE8300135W WO8400554A1 WO 1984000554 A1 WO1984000554 A1 WO 1984000554A1 DE 8300135 W DE8300135 W DE 8300135W WO 8400554 A1 WO8400554 A1 WO 8400554A1
Authority
WO
WIPO (PCT)
Prior art keywords
microfibers
molding compositions
molding
microfiber
compositions according
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.)
Ceased
Application number
PCT/DE1983/000135
Other languages
German (de)
English (en)
Inventor
Otto Kopp
Helmut Holzer
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.)
Sud-West-Chemie GmbH
Original Assignee
Sud-West-Chemie GmbH
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 Sud-West-Chemie GmbH filed Critical Sud-West-Chemie GmbH
Publication of WO1984000554A1 publication Critical patent/WO1984000554A1/fr
Priority to DK140184A priority Critical patent/DK140184A/da
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • 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

Definitions

  • the invention relates to granular, free-flowing, microfibers in the form of two- or three-dimensional fiber structures and to molding compositions containing binders, which are particularly suitable for injection molding of molded parts.
  • the invention relates to a method for producing such molding compositions and to their use.
  • thermosets or precursors thereof as binders, which, after they have completely hardened (usually in a hot form), are closely meshed, cross-linked, highly polymeric materials.
  • the molding compositions are mainly based on phenolic resins, urea resins, melamine resins, melamine-phenolic resins, polyester resins, epoxy resins and diallyl phthalate.
  • thermosetting molding compounds are reflected e.g. in their total consumption in Western Europe of about 325,000 tons in 1978 again.
  • the molded parts produced therefrom are widely used in the fields of the electrical industry, motor vehicle construction, aircraft construction, shipbuilding, rocket technology, chemical industry, office machines and household appliances.
  • the aim is to simplify the listening position of molded parts from molding compounds as much as possible and to carry them out in a safer and more environmentally friendly manner.
  • the use of a molding compound in the form of a free-flowing granulate is particularly suitable for this purpose, since this product form can be easily transported and metered within a processing device and, by avoiding dust, eliminates material losses and imposes a burden on the environment and personnel.
  • microfibers with a diameter of 0.002 to 0.015 mm and a minimum length of 0.4 mm in connection with a reinforcing resin, e.g. a phenol-formaldehyde resin has been reported (see European Patent Publication No. 0 047 701). These fibers are intended for the production of a material which protects against heat, a substrate consisting of the fibers being immersed in a solution of the said resin. So this is not a molding compound and a molded part made from it in the usual sense.
  • a reinforcing resin e.g. a phenol-formaldehyde resin
  • the invention is based on the object of specifying granulated, free-flowing, microfibers in the form of two- or three-dimensional fiber structures and molding compositions containing binders, in particular for injection molding, from which molded parts can be produced, the physical properties of which in relation to the special purpose of the respective molded part are improved compared to known molded parts. Examples of such physical properties are tensile strength, elongation at break, flexural strength, impact resistance, dimensional stability under heat, shrink resistance, thermal conductivity and electrical insulation.
  • microfibers have a maximum thickness of 0.02 mm and a maximum length of 1.0 mm and the fiber structures have a maximum diameter of 0.5 mm.
  • Molding parts can be produced from the molding compositions according to the invention which, in particular with regard to their mechanical properties, e.g. in the case of tensile, compressive, bending, impact or vibration loading, known molded parts which do not contain these special microfiber structures are superior.
  • the fiber structures have a diameter of at most 0.5 mm, preferably 0.1 mm.
  • the preferred maximum size of the fiber structures corresponds to fifty times this fiber diameter. But even at twenty or thirty times this diameter, satisfactory results are still achieved,
  • the fiber structures have a diameter of more than 0.5 mm, they can be deformed when the molding compound is injected into a mold. In this case, the optimal mechanical properties of the hardened molded parts are not achieved.
  • the cross section of the microfibers can be very different, for example approximately circular, elliptical, oval, triangular or quadrangular or polygonal or irregular. Hollow fibers may also be considered, which may have a longitudinal slot. _ 3 _
  • the microfiber can be arranged relatively regularly or very irregularly within a ball. Twisting of the individual fibers is also possible.
  • the cross-sectional circumference is of different lengths or the adhesive surface of the microfiber available for the contact between the binder of the molding composition and the microfiber is of different sizes.
  • microfibers are all the more preferred the longer the cross-sectional circumference or the larger the mentioned adhesive surface.
  • Inorganic fibers are e.g. Mineral fibers made of asbestos or calcium aluminum silicate, glass fibers or fibers made of carbon, such as graphite, or silicon carbide, silicon nitride, silicon dioxide, silica, zirconium oxide, zirconium silicate, boron, boron nitride, boron carbide, aluminum oxide or metals, such as steel, aluminum, magnesium, molybdenum or tungsten.
  • Mineral fibers made of asbestos or calcium aluminum silicate, glass fibers or fibers made of carbon, such as graphite, or silicon carbide, silicon nitride, silicon dioxide, silica, zirconium oxide, zirconium silicate, boron, boron nitride, boron carbide, aluminum oxide or metals, such as steel, aluminum, magnesium, molybdenum or tungsten.
  • organic fibers are natural fibers made of sisal, jute, hemp, henecen, cellulose fibers or palm fibers, and synthetic fibers such as fibers made of polyester, polyacrylonitrile, polypropylene, polyamide and aramid (polyamide with a high aromatic content).
  • the granules in which the molding compositions are present have a customary grain size.
  • the grain size is preferably approximately 2.5 mm.
  • the microfibers are largely individually present in the molding compositions, largely avoiding fiber bundles.
  • This has the advantage that each individual microfiber contributes to the reinforcement of the molding composition or of the molded part produced therefrom, with fewer microfibers being sufficient for a given degree of reinforcement than in the case in which fiber bundles are present, in which a large part the microfibers are ineffective.
  • the avoidance of fiber bundles leads also to reduce the cost of molding materials, as less microfibers are required if each one of them * contributes to improving the mechanical properties of the final cured product.
  • the microfibers have a length which corresponds approximately to fifty times the fiber thickness. On the one hand, this length brings with it a sufficiently large adhesive surface with respect to the binder of the molding composition for each microfiber and is also sufficient for the formation of the desired fiber structure. On the other hand, this length is not so great that when the molding compound is processed into molded parts, e.g. in injection molding, in the flow of the liquefied molding compound, the microfibers are mostly undesirably aligned.
  • the aforementioned ratio of the adhesive surface to the cross-sectional area of the microfiber can also be regarded as a measure of the length of the microfiber.
  • the stated minimum size of the adhesive surface expressed as a hundred times the cross-sectional area, results for microfibers with an essentially circular cross-section.
  • the stated ratio of adhesive surface to cross-sectional area can be approximately 150 to 230, in special cases even over 250. Microfibers with such large adhesive surfaces are particularly cheap.
  • the volume ratio of the molding compound binder (matrix) and the microfibers can be very different.
  • the ratio of the two volumes (matrix: microfiber) can e.g. about 3.2 (if the helix diameter corresponds to approximately five times the fiber diameter) to approximately 12.7 (if the helix diameter corresponds to ten times the fiber diameter).
  • This volume ratio can, however, also assume values outside the range mentioned for other coils. This depends on the number of turns of the helix and their mutual distance, for which there is a large scope within the scope of the invention. -
  • the material of the microfibers has a greater modulus of elasticity than the binder of the respective molding compound.
  • An important reason for the use of fibers in molding compositions is that, when mechanical forces act on the hardened molded part, the reinforcing fiber should relieve the surrounding resin matrix as much as possible, that is to say it should absorb as much tension as possible with as little deformation as possible. This is best achieved in that the fiber has a higher modulus of elasticity than the resin matrix to be reinforced. At the same time the self-evident prerequisite must be met that the adhesion
  • the binders of the molding compositions preferably consist of 10 to 50 percent by weight of microfibers. If less than 30 weight percent microfibers are used, only a slight reinforcing effect is achieved. The use of more than 50 percent by weight of microfibers leads to a noticeable increase in the cost of the molding compositions because of the relatively high cost of the microfibers, without a corresponding improvement in quality being achieved.
  • the molding compositions contain, as a binder or resin matrix, in which the microfibers are distributed, preferably a precondensed, prepolymerized or pre-added organic resin.
  • Such resins have the advantage that, depending on the molding process to which the molding compositions are subjected, they can be adjusted with regard to the extent of the pre-crosslinking. With these deformation processes, e.g. in injection molding, the crosslinking of the molding compound to the cured molded part is completed, i.e. Depending on the type of crosslinking reaction, the polycondensation, polymerization or polyaddition of the organic resin is completed.
  • the molding compounds can also contain other conventional constituents. These include e.g. Fillers or other auxiliary substances, e.g. can be liquid, powdery, granular, fibrous, carved or cord-like. Specific examples of this are wood flour, wood fibers, rock flour, such as chalk, kaolin, mica, talc and asbestos flour, asbestos
  • OMPI fibers Asbestos cords, lubricants, fluxes, dyes, color pigments and curing catalysts.
  • the molding compositions may also contain macrofibers which are already customary in molding compositions and whose dimensions exceed those of the microfibers.
  • microfibers used according to the invention can also be pretreated in a customary manner in order to increase the adhesion to the molding compound binder.
  • Suitable adhesion promoters are known (e.g. from "GLASS TECHNICAL REPORTS, JOURNAL FOR GLASS CUSTOMERS", Volume 37 (1964), No. 1, pages 1 to 15). It is e.g. around silanes or organic chromium complexes.
  • the coupling agent is normally applied to the fibers, e.g. Glass fibers, applied directly during fiber production in the form of a so-called "size" or as part of a final treatment of the fibers.
  • adhesion promoters that are not applied to the fibers, but be reasonably added as a mixture component the shape-.
  • the molding compositions can drive are manufactured according to the inventive Ver ⁇ , which is characterized in that interferes during the production of the respective molding material underlying the binder or the resin matrix microfibers in the binder or the resin ⁇ matrix or thereof in a preliminary stage.
  • the procedure has the advantage that the microfibers can be incorporated if the binder or resin on which the molding composition is based has a relatively low viscosity, which permits a uniform distribution of the fiber structures without substantial deformation.
  • microfibers at low viscosity not only promotes good wetting of the fibers with the resin and thus increased adhesion between the two, but also facilitates the uniform distribution of the microfibers in the molding composition while avoiding localized fiber accumulations.
  • the microfibers can be added during the condensation reaction of a phenolic resin in a process stage in which the viscosity of the resin is not yet too high.
  • the viscosity should not be too low to avoid segregation of the resin-microfiber system.
  • microfibers are incorporated into the molding compositions before other reinforcement
  • OMPI Components for example macro fibers, are supplied to the molding composition.
  • the molding compositions according to the invention can also be regarded as an improved preliminary stage for the production of the final molding composition which also contains further reinforcing agents, as mentioned above in connection with the additives.
  • Resin of the molding compound can be made, for example, by means of a roller mill with a gap width of approximately 0.5 mm or less.
  • the microfibers can also, for. B. in a S the low viscosity resin trom be introduced.
  • the aforementioned molding compositions are used for the production of molded parts.
  • the production processes include, for example the customary processes for processing molding compositions, such as injection molding, injection molding and simple pressing, into consideration.
  • microfibers are particularly evident here, since the small dimensions of these fibers or the fiber structures ensure that the original fiber structure is maintained. A deformation and / or alignment of the fiber structures with the consequence of non-optimal physical properties of the hardened molded parts is thus avoided.
  • the molding compositions are fed as granules to an injection molding device, melted there and at a temperature of about 150 ° C.-190 ° C. injected into a hot mold under pressure. This supply of heat completes the crosslinking that has already taken place to a certain extent in the molding composition, the desired cured one
  • the hardened molding compound then represents a thermosetting material which can no longer be liquefied by renewed heating, but decomposes when there is a strong supply of heat.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

La matière moulable contient un produit fibreux sous la forme de microfibres granulées et coulantes en deux ou en trois dimensions, ainsi qu'un liant, en particulier pour le moulage par injection de pièces de forme. Les microfibres présentent une épaisseur maximale de 0,02 mm et une longueur maximale de 1,0 mm, et le produit fibreux un diamètre maximal de 0,5 mm. La matière moulable améliore les caractéristiques physiques des pièces de forme, telles que la résistance à la traction, l'allongement à la rupture, la réistance à la flexion, la résilience, la stabilité de la forme à la chaleur, la résistance au retrait, la conductibilité thermique et l'isolation électrique.
PCT/DE1983/000135 1982-08-03 1983-08-03 Matiere moulable contenant un produit fibreux sous la forme de microfibres en deux ou en trois dimensions Ceased WO1984000554A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK140184A DK140184A (da) 1982-08-03 1984-02-29 Formemasse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19823228989 DE3228989C2 (de) 1982-08-03 1982-08-03 Granulierte, rieselfähige Formmassen

Publications (1)

Publication Number Publication Date
WO1984000554A1 true WO1984000554A1 (fr) 1984-02-16

Family

ID=6170033

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1983/000135 Ceased WO1984000554A1 (fr) 1982-08-03 1983-08-03 Matiere moulable contenant un produit fibreux sous la forme de microfibres en deux ou en trois dimensions

Country Status (4)

Country Link
EP (1) EP0126083A1 (fr)
DE (1) DE3228989C2 (fr)
DK (1) DK140184A (fr)
WO (1) WO1984000554A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0173559A1 (fr) * 1984-08-31 1986-03-05 Minnesota Mining And Manufacturing Company Connection ininflammable de câbles
EP0178561A3 (en) * 1984-10-17 1987-10-21 Bayer Ag Resin granules containing fillers
EP0319924A3 (fr) * 1987-12-08 1991-03-20 Idemitsu Petrochemical Company Limited Procédé de préparation de résine thermoplastique
US7493702B2 (en) 2005-10-17 2009-02-24 Hilti Aktiengesellshaft Tilt control method

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100886303B1 (ko) * 2003-03-19 2009-03-04 니폰덴신뎅와 가부시키가이샤 광강도변조기
KR100749555B1 (ko) * 2003-07-16 2007-08-16 니폰 덴신 덴와 가부시끼가이샤 광도파로 재료 및 광도파로

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB618094A (en) * 1945-10-19 1949-02-16 Du Pont Plastic compositions containing glass fibres
DE1504343A1 (de) * 1962-08-28 1970-02-26 Ver Flugtechnische Werke Verfahren zur Herstellung von Werkstoffen hoher Festigkeit
NL7105691A (en) * 1971-04-27 1971-07-26 Rutile filler for plastics
DE2611974A1 (de) * 1976-03-20 1977-09-29 Bayer Ag Neue verstaerkte kunststoffe und verfahren zu ihrer herstellung
DE2811954A1 (de) * 1977-03-28 1978-10-12 Skf Kugellagerfabriken Gmbh Verfahren zur herstellung eines stossfesten mehrkomponentenwerkstoffs
EP0050377A1 (fr) * 1980-10-16 1982-04-28 Rütgerswerke Aktiengesellschaft Matériau de friction sans amiante

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1544661A1 (de) * 1965-10-28 1969-05-14 Basf Ag Formmassen fuer die Herstellung von Kunsstoffartikeln
US3598693A (en) * 1967-09-05 1971-08-10 Monsanto Co Molding composition
JPS4919097B1 (fr) * 1970-12-29 1974-05-15
DE2144687C3 (de) * 1971-09-07 1976-01-02 Gerhard Dipl.-Chem. Dr. 6114 Gross Umstadt Illing Verwendung von härtbaren Epoxydharzen, als Zusatz zu thermoplastischen Kunstharzmassen
DE2423852A1 (de) * 1974-05-16 1975-12-04 Siemens Ag Giessling aus reaktionsharz
DE2454221C2 (de) * 1974-11-15 1985-03-21 Bayer Ag, 5090 Leverkusen Neue verstärkte Kunststoffe und Verfahren zu ihrer Herstellung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB618094A (en) * 1945-10-19 1949-02-16 Du Pont Plastic compositions containing glass fibres
DE1504343A1 (de) * 1962-08-28 1970-02-26 Ver Flugtechnische Werke Verfahren zur Herstellung von Werkstoffen hoher Festigkeit
NL7105691A (en) * 1971-04-27 1971-07-26 Rutile filler for plastics
DE2611974A1 (de) * 1976-03-20 1977-09-29 Bayer Ag Neue verstaerkte kunststoffe und verfahren zu ihrer herstellung
DE2811954A1 (de) * 1977-03-28 1978-10-12 Skf Kugellagerfabriken Gmbh Verfahren zur herstellung eines stossfesten mehrkomponentenwerkstoffs
EP0050377A1 (fr) * 1980-10-16 1982-04-28 Rütgerswerke Aktiengesellschaft Matériau de friction sans amiante

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Additives for Plastics, Volume 1, 1978, New York N.Y. (US) J. MILEWSKI: "Whiskers and Microfibers", pages 79-122, see pages 101-119 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0173559A1 (fr) * 1984-08-31 1986-03-05 Minnesota Mining And Manufacturing Company Connection ininflammable de câbles
EP0178561A3 (en) * 1984-10-17 1987-10-21 Bayer Ag Resin granules containing fillers
EP0319924A3 (fr) * 1987-12-08 1991-03-20 Idemitsu Petrochemical Company Limited Procédé de préparation de résine thermoplastique
US7493702B2 (en) 2005-10-17 2009-02-24 Hilti Aktiengesellshaft Tilt control method

Also Published As

Publication number Publication date
DK140184A (da) 1984-04-03
EP0126083A1 (fr) 1984-11-28
DK140184D0 (da) 1984-02-29
DE3228989C2 (de) 1984-11-22
DE3228989A1 (de) 1984-02-09

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