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
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
• • 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
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
  • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron

Definitions

• the present invention relates to glass threads (or "fibers") capable of reinforcing organic and / or inorganic materials and usable as textile threads, these threads being capable of being obtained by the process which consists in mechanically drawing glass threads melt 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 new composition which is particularly advantageous for forming fine strands.
• glass wires whose permittivity and dielectric losses are low, in particular for forming light fabrics which are used to reinforce printed circuit supports.
• These supports consist mainly of a reinforcement, in particular glass strands, and of a resin on which there are various electrical and / or electronic components.
• the dielectric properties of this support become decisive. If these properties do not perform as expected, risks of overheating and / or distortion of the signals may appear. Furthermore, to contribute to miniaturization, wires of ever smaller diameter are sought to reduce the thickness and improve the flatness of the 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, polyesters, 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 represented here by the glass strands according to the present invention, which generally occupy approximately 60% of the volume.
• a glass subjected to an alternating current transforms part of it into electrical energy dissipated in the material.
• This electrical energy is known as dielectric loss.
• the 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.
• W is the electrical energy dissipated in the glass or dielectric losses
• k is a constant
• f is the frequency
• v is a potential gradient
• ⁇ is the permittivity
• tan ⁇ is the tangent of the angle of dielectric loss or dielectric dissipation factor.
• the object of the present invention is to propose new glass compositions for forming reinforcing wires which have dielectric properties of the same order of magnitude as those of known glasses in the MHz range and which simultaneously exhibit improved dielectric properties in the range. of the GHz for a smaller wire diameter, while having satisfactory fiberizing properties for obtaining reinforcing wires under economical conditions.
• the glass strands in question can be fibers under conditions causing the least possible breakage.
• the dielectric properties as being for the "MHz range” a frequency range in which the characterizations of the dielectric properties of the glasses are carried out, in particular at 1 MHz, and for the "GHz range", a frequency range in which are carried out characterizations of the dielectric properties of the glasses, in particular at 9.5 GHz.
• T ⁇ q the liquidus temperature
• iq is more than 100 ° C, preferably more than 300 ° C lower than T (log ⁇ 3).
• 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 O 3 -CaO, in particular the strands designated under the name of strands E glass, the archetype of which is described in US Pat. Nos. 2,334,981 and US Pat. No. 2,571,074.
• the E glass strands 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.
• 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-A-96/39363 and WO-A-99/52833. These compositions, although having acceptable dielectric losses in the MHz and GHz range, are not satisfactory for forming fine wires because the breakage rate during fiberizing remains high.
• compositions are capable of giving reinforcement threads under economically satisfactory fiberizing conditions and make it possible to achieve good dielectric performance in the GHz range. . It seems that the high level of performance is due to the presence of P 2 O in the compositions. If the addition of P 2 O 5 proves beneficial for the dielectric properties, it also increases the risk of demixing with the consequence of forming a heterogeneous glass which breaks more easily during fiberizing.
• zirconium oxide, ZrO 2 in a composition based on the combination SiO 2 -AI 2 ⁇ 3 -B 2 O 3 makes it possible to obtain wires of small diameter, in particular smaller or equal to 10 ⁇ m, preferably less than or equal to 7 ⁇ m, or even of the order of 5 ⁇ m, in good fiberizing conditions with a reduced breakage rate, while retaining acceptable dielectric properties in the range of MHz and GHz.
• 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%
• compositions according to the invention have an acceptable liquidus temperature, in particular less than or equal to 1150 ° C., without any major risk of devitrification during drawing in cold zones of the drawing crucible and in the channels leading the glass from the oven to the drawing crucibles. fiber drawing.
• 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
• Alumina, AI 2 O 3 also constitutes a former of the network of glasses according to the invention and plays a very important role with regard to the hydroiytic resistance of these glasses.
• the decrease in the percentage of this oxide below 10% results in a significant increase in the hydroiytic 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 rate of Al 2 ⁇ 3 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 than 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 addition of zirconium oxide, ZrO 2 appears to be an essential point of the invention.
• the level of ZrO 2 is between 0.5 and 1.5%, preferably is less than or equal to 1%. This oxide appears to play a very important role on the dielectric properties, more particularly in the GHz range as indicated later in the examples. However, the content should be limited to
• alkaline earth oxides lime and magnesia
• the limits defined in alkaline earth oxides, lime and magnesia make it possible to adjust the viscosity 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%.
• Alkalis in particular Na 2 O and K 2 O can be introduced into the compositions of the glass strands according to the invention to limit devitrification and possibly reduce the viscosity of the glass.
• the content of alkaline oxides Na 2 O + K 2 O + Li 2 O must however remain less than or equal to 2% to avoid deterioration of the dielectric properties and a penalizing decrease in the hydroiytic 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 alkaline oxide (from Na 2 O, K 2 O and Li 2 O) or may contain a combination of at least two alkaline 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 hydroiytic 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 glass fibers E.
• Fluorine, F can be added in small quantities to improve fusion glass in particular from 0.5 to 2%, or be present in an impurity state, in particular from 0.1 to 0.5%.
• Titanium oxide, TiO 2 can also be introduced in an amount which can represent up to 3% of the composition, preferably less than 2 % or even less than 1%. It makes it possible to lower the viscosity without appreciable degradation of the dielectric losses.
• the possible content of Fe 2 O 3 is rather to be considered as a content of impurities, frequently encountered in this family of compositions.
• any percentage of a constituent of the composition should be understood as a weight percentage, and the compositions according to the invention may contain up to 2 or 3% of compounds to be considered as non-analyzed impurities (for example example SrO, SO 3 , MnO, MnO 2 ), as 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, in particular for forming light fabrics composed of strands of diameter less than or equal to 10 ⁇ m, preferably less than or equal to 7 ⁇ m, and advantageously of around 5 ⁇ m.
• 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 weight percentages: SiO 2 50 to 60%, preferably SiO 2 > 52% and / or SiO 2 ⁇ 57% AI 2 O 3 10 to 19%, preferably AI 2 O 3 > 13% and / or AI 2 O 3 ⁇ 17%
• 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%
• R 2 O ⁇ 2% preferably R 2 O ⁇ 1%
• RO 4 to 15% preferably RO> 6% and / or RO ⁇ 10%
• Comparative examples denoted A and B also appear in Table 1. They correspond to the following glasses: A: DB glass: glass according to patent application WO 99/52833 In these examples, yarns composed of glass filaments having a diameter of 7 ⁇ m (examples 1, 2 and B) and 10 ⁇ m (example A) are obtained by drawing molten glass, the glass has the composition mentioned in the table 1, expressed as percentages by weight. When the total sum of the contents of all the compounds is slightly less than or greater than 100%, it should be understood that the residual level corresponds to the impurities, non-analyzed minority components (level of at most 1 to 2%) and / or is due to the approximation accepted in this area in the analysis methods used.
• T (log ⁇ 3) the temperature at which the viscosity of the glass is
• T iq the liquidus temperature of the glass, corresponding to the temperature at which the most refractory phase, which can devitrify in the glass, has a zero growth rate and thus corresponds to the melting temperature of this devitrified phase.
• Measurements at 1 MHz are carried out in a traditional manner, known to those skilled in the art for this type of metrology.
• the 9.5 GHz measurements 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. This method allows for precise results in very high frequency.
• Table 1 also shows the number of complete yarn spools formed per day under the conditions mentioned above. This number makes it possible to have a measure of appreciation of the fiberizing performance comparable for the different glasses.
• 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 and 9.5 GHz.
• the dielectric properties of glass D are remarkably close, while lowering the fiber-drawing temperature of the glasses according to the invention in comparison with that of glass D.
• the glasses according to the invention are also remarkable in that they make it possible to form wires of small diameter with a particularly advantageous yield.
• the number of complete spools of wire is better with the glasses according to the invention than with the glasses according to WO 99/52833 (+ 36%) for an identical diameter of filaments, and considerably higher (+ 300%) than 'with glass D, and this for a much smaller diameter (7 ⁇ m instead of 10 ⁇ m).
• 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.
• the glass strands according to the invention have the advantage of being able to be obtained with a better yield and a lower cost than the known glass strands.
• the glass strands according to the invention are useful for forming light fabrics having good flatness, which is particularly sought after in electronic 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)
• Reinforced Plastic Materials (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (2)

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• 2003
  • 2003-03-13 FR FR0303206A patent/FR2852311B1/fr not_active Expired - Fee Related
• 2004
  • 2004-03-10 KR KR1020057017139A patent/KR101043193B1/ko not_active Expired - Fee Related
  • 2004-03-10 US US10/548,581 patent/US7612002B2/en not_active Expired - Fee Related
  • 2004-03-10 EA EA200501451A patent/EA008278B1/ru not_active IP Right Cessation
  • 2004-03-10 MX MXPA05009705A patent/MXPA05009705A/es unknown
  • 2004-03-10 EP EP04718986A patent/EP1601624B1/fr not_active Expired - Lifetime
  • 2004-03-10 WO PCT/FR2004/000568 patent/WO2004083142A2/fr not_active Ceased
  • 2004-03-10 JP JP2006505709A patent/JP4695066B2/ja not_active Expired - Fee Related
  • 2004-03-10 AT AT04718986T patent/ATE356095T1/de active
  • 2004-03-10 ES ES04718986T patent/ES2283995T3/es not_active Expired - Lifetime
  • 2004-03-10 CN CNB2004800067504A patent/CN100564298C/zh not_active Expired - Fee Related
  • 2004-03-10 DE DE602004005165T patent/DE602004005165T2/de not_active Expired - Lifetime

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