Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
  • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
  • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
  • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
  • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
  • Y10T428/249942—Fibers are aligned substantially parallel
  • Y10T428/249947—Polymeric fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

• the present invention relates to "reinforcing" glass yarns (or “fibers”), that is to say usable for reinforcing organic and / or inorganic materials and usable as textile yarns, these yarns being capable of being obtained by the process which consists in mechanically stretching molten glass streams flowing from orifices arranged at the base of a die generally heated by the Joule effect.
• the present invention relates more specifically to glass strands with low dielectric constants having a particularly advantageous new composition.
• glass wires whose permittivity and dielectric losses are low, used mainly in the form of fabrics, to reinforce printed circuit supports.
• the latter consist mainly of a reinforcement, in particular glass strands, and of a resin on which there are various electrical and / or electronic components.
• the polymers traditionally used for printed circuit boards are essentially made of epoxy resin.
• Polymers with better dielectric properties are known today, in particular polyimide resins, cyanate ethers, polyester, or even PTFE, the dielectric properties of which are satisfactory.
• the improvement of the dielectric properties of a printed circuit board must therefore essentially relate to the improvement of the properties of the reinforcement, wires of The improvement of the dielectric properties of a printed circuit board must therefore essentially relate to the improvement of the properties of the reinforcement, glass strands in the context of the present invention, which generally occupy approximately
• dielectric losses are proportional to the permittivity and to the tangent of the angle of loss (tan ⁇ ) which depend on the composition of the glass for a given frequency. Dielectric losses are expressed in the form (see for example: J.C. Dubois, in “” Engineering Techniques “, treated” Electronics “, chapter E 1850:” dielectric properties of polymers ").
• W k.fV. ⁇ .tan ⁇
• W is the electrical energy dissipated in the glass or dielectric losses
• k a constant
• f the frequency
• v a potential gradient
• ⁇ the permittivity
• tan ⁇ the tangent of the dielectric loss angle or dielectric dissipation factor.
• the glass strands in question have good hydrolytic resistance properties.
• - "MHz range” as being a frequency range in which the characterizations of the dielectric properties of the glasses are carried out, in particular at 1 MHz
• GHz range as being a frequency range in which the characterizations of the dielectric properties of the glasses are carried out, in particular at 10 GHz
• the value of ⁇ is low, preferably less than 6, or even less than or equal to 5.
• the liquidus temperature gives the upper limit of the temperature zone where the glass may tend to devitrify.
• iq is more than 100 ° C, preferably more than 300 ° C lower than T (log ⁇ 3).
• ⁇ - hydrolytic resistance means the ability of a glass to dissolve by leaching.
• This property is determined by measuring the weight loss of finely ground glass powders (between 360 and 400 ⁇ m) after staying in water maintained at the boiling point for five hours (10 g of glass in 100 ml of water). After rapid cooling, the solution is filtered and part of the filtrate is weighed after evaporation. The quantity of glass extracted ("leached" glass; in mg) is thus determined per gram of glass tested, which is denoted "DGG". The lower the DGG value, the more resistant the glass is to hydrolysis. A glass is considered to have good hydrolytic resistance if the value of DGG is less than 25, and excellent if the value is less than 10.
• the most commonly used reinforcing glass strands are thus the strands formed from glass which derive from the eutectic at 1170 ° C. of the ternary diagram SiO 2 -AI 2 ⁇ 3-CaO, in particular the strands designated under the name of strands glass E, the archetype of which is described in patents US-A-2,334,981 and US-A-2,571,074.
• the strands of glass E have a composition essentially based on silica, alumina, lime and boric anhydride. Boric anhydride, present at levels ranging in practice from 5 to 13% by weight in the glass compositions qualified "glass E", replaces part of the silica.
• Glass strands E are further characterized by a limited content of alkaline oxides (essentially Na 2 O and / or KO). Their dielectric properties are insufficient in view of the new requirements for printed circuit supports.
• Glasses D Another family of glass strands is known and obtained from compositions very rich in silica and boron.
• compositions have recently been proposed which make it possible to obtain advantageous dielectric properties and relatively economical fiberizing conditions. These compositions are in particular described in applications WO 99/39363 and WO 99/52833.
• compositions although very interesting by their dielectric properties measured in the MHz range, exhibit high dielectric losses in the GHz range, as shown by the results reported in Table I.
• the glass strands according to the invention are obtained from a composition essentially comprising the following constituents, within the limits defined below, expressed in percentages by weight: SiO 2 50 to 60%
• the invention therefore proposes a new family of compositions selected to obtain good dielectric properties in the MHz range. Surprisingly, it is noted that the compositions according to the invention also have good dielectric properties in the GHz range.
• compositions according to the invention have a very low liquidus temperature, in particular less than or equal to 1000 ° C. This results in a substantial reduction in the risks of devitrification during drawing in cold zones of the drawing crucible and in the channels leading the glass from the furnace to the drawing crucibles.
• compositions according to the invention exhibit good hydrolytic resistance, with in particular DGG values of less than 10.
• Silica is one of the oxides which forms the network of glasses according to the invention and plays an essential role for their stability.
• the silica content, SiO 2 , of the selected compositions is between 50 and 60%, in particular greater than 52%, and / or in particular less than or equal to 57%.
• Alumina also constitutes a trainer of the network of glasses according to the invention and plays a very important role with regard to the hydrolytic resistance of these glasses.
• the decrease in the percentage of this oxide below 10% results in a significant increase in the hydrolytic attack of the glass while too large an increase in the percentage of this oxide entails risks of devitrification and an increase in viscosity.
• the level of alumina, Al 2 0 3 l of the selected compositions is between 10 and 19%, in particular greater than or equal to 13% and / or in particular less than or equal to 17%.
• the level of lime, CaO, of the selected compositions is less than or equal to 10%, in particular less than or equal to 8%, or even even less than or equal to 6% and / or preferably greater than or equal to 2%, even even greater or equal to 4%.
• the level of magnesia, MgO, of the selected compositions is less than or equal to 10%, in particular less than or equal to 8%, or even even less than or equal to 6% and / or preferably greater than or equal to 2%.
• the P 2 O 5 is between 0.5 and 4%, preferably greater than or equal to 1% and / or preferably less than or equal to 3%, or even less than or equal to 2%.
• This oxide appears to play a very important role on the dielectric properties, in particular in the range of the GHz as the results presented later prove it.
• the limits defined in alkaline earth oxides, lime and magnesia make it possible to adjust the viscosity and control the devitrification of the glasses according to the invention. Good fiberizing ability is obtained by choosing the sum of these alkaline earth oxides between 4 and 15%, preferably greater than or equal to 6% and / or preferably less than or equal to 10%.
• CaO appears to have a beneficial contribution on hydrolytic resistance.
• Alkalis in particular sodium hydroxide, Na 2 O, and potassium hydroxide, K 2 O, can be introduced into the compositions of the glass strands according to the invention in order to limit devitrification and possibly reduce the viscosity of the glass.
• the content of alkaline oxides Na2 ⁇ + K 2 O + Li 2 O must however remain less than or equal to 2% to avoid deterioration of the dielectric properties and to avoid a penalizing decrease in the hydrolytic resistance of the glass.
• the level of alkalis is generally greater than 0.1%, due to the presence of impurities contained in the raw materials carrying other constituents and it is preferably less than or equal to 1%, or even 0.5%, or even 0.3%.
• the composition may contain a single alkali metal oxide (from Na 2 O, K 2 O and LÎ 2 O) or may contain a combination of at least two alkali metal oxides, the content of each alkali being less than or equal to 1.5%, preferably less than or equal to 0.8%.
• the boron content is between 16 and 25%, preferably greater than or equal to 18% and / or preferably less than or equal to 22%, or even less than or equal to 20%. According to a preferred version of the invention, it is desired to limit this oxide to moderate contents compared to those of glass D on the one hand so as not to degrade the hydrolytic resistance and on the other hand because the price of the raw materials carrying boron is high. Boron can be introduced in a moderate amount by the incorporation, as a raw material, of waste glass fibers comprising boron, for example waste glass fibers E.
• Fluorine, F 2 can be added in small amounts to improve the melting of the glass, in particular by 0.5 to 2%, or be present in the state of impurity, in particular from 0.1 to 0.5%.
• the possible contents of ⁇ O 2 , and / or Fe 2 ⁇ 3 are rather to be considered as contents of impurities, frequently encountered in this family of compositions.
• TiO 2 can reach contents of between 2 and 3%, but is preferably less than 2%, or even less than 1%.
• any percentage of a constituent of the composition must be understood as a weight percentage, and the compositions according to the invention can contain up to 2 or 3% of compounds to be considered as non-analyzed impurities, such as this is known in this kind of composition.
• the invention also relates to composites formed from glass strands and organic material in which the reinforcement is provided at least by the glass strands of compositions defined above.
• Such glass strands are used for the manufacture of printed circuit support.
• the invention also relates to a process for manufacturing glass strands of compositions defined above according to which a multiplicity of molten glass strands is drawn, flowing from a multiplicity of orifices arranged at the base of one or more dies, in the form of one or more layers of continuous filaments, then the filaments are gathered into one or more threads which are collected on a moving support.
• the molten glass supplying the orifices of the die (s) has the following composition, expressed in percentages by weight:
• AI2O3 10 to 19% preferably AI 2 O 3 > 13% and / or AI 2 O 3 ⁇ 17% B 2 O 3 16 to 25%
• RO 4 to 15% preferably RO> 6% and / or RO ⁇ 10%
• the invention also relates to glass compositions suitable for producing reinforcing glass strands comprising the following constituents, within the limits defined below, expressed in percentages by weight:
• AI 2 O 3 10 to 19% preferably AI 2 O 3 > 13% and / or AI 2 O 3 ⁇ 17% B 2 O 3 16 to 25%
• RO 4 to 15% preferably RO> 6% and / or RO ⁇ 10%
• glass strands composed of glass filaments 14 ⁇ m in diameter are obtained by drawing molten glass, the glass has the composition mentioned in Table I, expressed in weight percentages.
• the 1 MHz measurements are carried out in a traditional manner, known to those skilled in the art for this type of metrology.
• the measurements at 10 GHz were carried out according to the method described by WB Westphal ("Distributed Circuits", in “Dielectric materials and applications”, the Technology Press of MIT and John Wiley & Sons, Inc. New York, Chapman & Hall, Ltd , London, 1954. See in particular p. 69).
• the principle of this method is based on the measurement of the dielectric properties of a sample in the form of a disc, placed against a waveguide.
• the dielectric properties of the compositions according to the invention are of the same order of magnitude as those of the compositions according to WO 99/52833 for measurements at 1 MHz.
• the glasses according to the invention have excellent hydrolytic resistance.
• the glass strands according to the invention are advantageously suitable for all the usual applications of conventional glass strands E and can be substituted for glass strands D for certain applications.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Glass Compositions (AREA)

Applications Claiming Priority (3)

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• 2001
  • 2001-05-23 FR FR0106859A patent/FR2825084B1/fr not_active Expired - Fee Related
• 2002
  • 2002-05-02 CN CNA028104773A patent/CN1511120A/zh active Pending
  • 2002-05-02 EP EP02730379A patent/EP1390313A1/fr not_active Withdrawn
  • 2002-05-02 US US10/478,616 patent/US20040175557A1/en not_active Abandoned
  • 2002-05-02 RU RU2003136776/03A patent/RU2003136776A/ru not_active Application Discontinuation
  • 2002-05-02 WO PCT/FR2002/001509 patent/WO2002094728A1/fr not_active Ceased
  • 2002-05-02 MX MXPA03010595A patent/MXPA03010595A/es not_active Application Discontinuation
  • 2002-05-02 JP JP2002591405A patent/JP2004525066A/ja active Pending

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