Classifications

• • 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
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/40—Organo-silicon compounds
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D1/00—Woven fabrics designed to make specified articles
• • D—TEXTILES; PAPER
  • D03—WEAVING
  • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
  • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
  • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
  • D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
  • D03D15/267—Glass
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
  • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
  • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
• • 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

Definitions

• This disclosure relates to glass cloth, prepregs, printed wiring boards, etc.
• Patent Documents 1 and 2 describe a prepreg obtained by impregnating glass cloth with a low-dielectric thermosetting resin (hereinafter collectively referred to as "matrix resin") that is crosslinked by a radical reaction using a polyphenylene ether or other resin whose ends are modified with vinyl or methacryloxy groups and hardens, and then drying the resin.
• matrix resin a low-dielectric thermosetting resin
• a laminate is known that is made by stacking the prepregs obtained in this way and hardening them through heating and pressure.
• Patent Documents 1 and 2 aim to achieve a low dielectric constant and low dielectric dissipation factor for the laminate by combining the prepreg with glass cloth, which has a low dielectric constant and low dielectric dissipation factor.
• Patent Documents 3 and 4 report that the amount of silanol groups on the glass surface is reduced by heating the silica glass cloth at high temperatures.
• Patent Document 5 also reports that the silanol groups present on the glass cloth surface are reduced by surface treatment, thereby reducing the dielectric loss tangent of the glass cloth.
• Patent Document 6 also reports a method of packaging quartz glass cloth to prevent the dielectric loss tangent of the quartz glass cloth from increasing over time.
• the present disclosure aims to provide a glass cloth that can achieve excellent dielectric properties, suppress an increase in dielectric loss tangent over time, and achieve excellent solder heat resistance in a resin substrate produced using the glass cloth.
• Another object of the present disclosure is to provide a prepreg and a printed wiring board that are realized using the glass cloth, and to provide a method for producing the glass cloth.
• One aspect of the present invention is as follows.
• a glass cloth made by weaving glass yarn, the glass cloth is surface-treated with a surface treatment agent, a difference between the dielectric loss tangent of the glass cloth at 10 GHz and the bulk dielectric loss tangent of the glass constituting the glass yarn at 10 GHz (the dielectric loss tangent - the bulk dielectric loss tangent) is less than 0.00000;
• the glass cloth has 10 or less white spots per square meter.
• the glass cloth according to item 1 wherein the silicon (Si) content in the glass yarn is 95.0 to 100% by mass in terms of silicon dioxide (SiO 2 ).
• SiO 2 silicon dioxide
• the glass cloth according to item 1 or 2 wherein the average degree of opening calculated from the yarn width of each of the warp yarns and the weft yarns of the glass cloth is more than 40%.
• the glass cloth according to any one of items 1 to 3 wherein the bulk dielectric loss tangent is 0.002 or less.
• the surface treatment agent comprises a silane coupling agent.
• the molecular weight of the silane coupling agent is 250 to 1,000.
• the surface treatment agent contains two or more silane coupling agents having different molecular weights.
• Item 9 The glass cloth according to any one of items 1 to 8, wherein the glass cloth has an ignition loss value of 0.01 to 0.5% by mass.
• 10 10.
• a prepreg comprising the glass cloth according to any one of items 1 to 10 and a thermosetting resin.
• Item 12. A printed wiring board comprising the prepreg according to item 11.
• Item 13. An integrated circuit comprising the printed wiring board according to item 12.
• Item 13. An electronic device comprising the printed wiring board according to item 12.
• the surface treatment step includes: controlling the temperature and pH of the surface treatment solution; Item 17.
• Item 18 The method for producing a glass cloth according to any one of Items 15 to 17, further comprising a step of subjecting the glass yarns to an opening treatment after the surface treatment step.
• Item 19 The method for producing a glass cloth according to any one of Items 15 to 18, further comprising inspecting the glass cloth for white spots after the surface treatment step.
• the present disclosure it is possible to provide a glass cloth that can achieve excellent dielectric properties, suppress an increase in the dielectric loss tangent over time, and achieve excellent solder heat resistance in a resin substrate produced using the glass cloth. Furthermore, according to the present disclosure, it is possible to provide a prepreg, a printed wiring board, an integrated circuit, and an electronic device that are realized using the glass cloth, and to provide a method for manufacturing the glass cloth, etc.
• 5A and 5B are diagrams for explaining white spots in the present embodiment.
• the structures when multiple structures represented by the same symbol exist in the same formula, unless otherwise specified, the structures may be independently selected and may be the same or different from each other. When multiple structures represented by the same symbol exist in different formulas, the structures may be independently selected and may be the same or different from each other, unless otherwise specified.
• various measurements are performed based on the methods described in the Examples unless otherwise specified.
• the upper or lower limit of a numerical range described in stages may be replaced by the upper or lower limit of a corresponding numerical range described in another stage, and may also be replaced by the corresponding value described in the Examples.
• process includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the function of the process is achieved.
• the scale, shape, and length may be exaggerated for clarity.
• the glass cloth of this embodiment is a glass cloth made by weaving glass yarns, for example, a glass cloth made by weaving glass yarns made of a plurality of glass filaments as warp and weft yarns.
• the glass cloth is surface treated with a surface treatment agent.
• the difference between the dielectric loss tangent of the glass cloth at 10 GHz and the bulk dielectric loss tangent of the glass constituting the glass yarn at 10 GHz is less than 0.00000;
• the number of white spots is 10 or less per square meter (for example, 10.0 or less per square meter).
• the glass cloth of this embodiment is suitable as a constituent material for making prepregs, printed wiring boards, integrated circuits, electronic devices, etc.
• the inventors focused on glass cloth that had been surface-treated after being heated to deoiling at high temperatures.
• the inventors were the first to discover that glass cloth with a dielectric tangent lower than the bulk tangent has an extremely low amount of silanol groups on the glass surface, making it difficult for the cloth to adsorb moisture present in the storage environment. Therefore, it is possible to suppress the increase in the dielectric tangent of the glass cloth over time without the need for special packaging.
• the glass cloth of this embodiment by finding a method for stably dispersing in water even a surface treatment agent (e.g., a certain silane coupling agent) that has poor dispersibility and/or compatibility in water, it is possible to improve the appearance quality.
• a surface treatment agent e.g., a certain silane coupling agent
• the glass cloth of this embodiment preferably has a dielectric loss tangent at 10 GHz of 0.0020 or less.
• a glass cloth can provide a prepreg and a printed wiring board with improved dielectric properties.
• the dielectric loss tangent of the glass cloth at 10 GHz is preferably 0.0015 or less, 0.0010 or less, 0.0007 or less, 0.0006 or less, 0.0005 or less, 0.0004 or less, 0.0003, 0.0002, 0.00019, 0.00018, 0.00017, 0.00016, 0.00015, 0.00014, 0.00013, 0.00012, or 0.00011 or less.
• the dielectric loss tangent of the glass cloth may be greater than 0.
• the dielectric loss tangent at 10 GHz of the glass cloth of this embodiment is measured by a method using a split cylinder resonator (a method using a resonance method), specifically, by the method described in the Examples.
• This method allows for simpler and more accurate measurement than conventional methods in which a substrate is fabricated as a measurement sample and the dielectric properties are evaluated.
• the reason for this, without being limited by theory, is that the resonance method is suitable for evaluation in the high frequency range, particularly for evaluation of low-loss materials.
• other methods for evaluating dielectric properties include the lumped parameter method and the reflection transmission method.
• the lumped parameter method requires the measurement sample to be sandwiched between two electrodes to form a capacitor, which can be a problem in that the operation can be complicated. Furthermore, when evaluating low-loss materials, the reflection transmission method is subject to the strong influence of the port matching characteristics, making it difficult to accurately evaluate the dielectric loss tangent of the measurement sample. From the above, it is possible to easily and accurately measure the dielectric loss tangent of a glass cloth by using a technique that uses a resonance method, specifically, by using the technique described in the examples.
• a measuring instrument for measuring the dielectric properties thereof has a predetermined measurable range.
• the measuring equipment for measuring dielectric properties be capable of measuring frequencies of 10 GHz or higher. Measurable frequencies of 10 GHz or higher make it easier to evaluate characteristics in frequency band regions, particularly characteristics in frequency band regions expected when the material is actually used as glass cloth for printed wiring boards for high-speed communications.
• the area for measuring the dielectric properties is preferably 10 mm2 or more, more preferably 15 mm2 or more, and even more preferably 20 mm2 or more. This makes it easier to improve the reliability of the measurement results obtained, and therefore makes it easier to determine whether the measurement results obtained are within a predetermined reference value range.
• the thickness of the measurement sample is preferably 3 ⁇ m to 300 ⁇ m, more preferably 5 ⁇ m to 200 ⁇ m, and even more preferably 7 ⁇ m to 150 ⁇ m.
• the bulk dielectric loss tangent at 10 GHz of the glass raw materials constituting the glass cloth is measured by a method using a split cylinder resonator (a method using a resonance method), specifically, by the method described in Examples.
• the glass raw materials may be, for example, glass threads, glass filaments, glass seeds, etc.
• the bulk dielectric loss tangent at 10 GHz is preferably 0.002 or less, more preferably 0.0015 or less, even more preferably 0.001 or less, even more preferably 0.0005 or less, and particularly preferably 0.0004 or 0.0002 or less. This makes it easier to achieve the effects of the present disclosure.
• the dielectric loss tangent of the glass cloth is, for example, A method for removing deteriorated materials and residues present on the surface of glass fibers, and a method for surface treating glass fibers with a surface treatment agent capable of lowering the dielectric loss tangent of the glass cloth. It can be controlled by the following.
• one embodiment of the deteriorated product and the residue, etc. is, for example, the following (i) to (ii): (i) Degraded products of sizing agents that have physically adhered to the glass surface and are thermally oxidized. (ii) Residues of surface treatment agents that have physically adhered to the glass surface without forming a chemical bond with the surface and remain on the surface even after washing with water, or modified products thereof.
• the difference (Difference between dielectric loss tangent and bulk dielectric loss tangent) In the glass cloth of this embodiment, the difference (the dielectric loss tangent - the bulk dielectric loss tangent) is less than 0.00000. Such a relationship is achieved when the bulk dielectric loss tangent is greater than the dielectric loss tangent by more than 0.00000.
• the methods for measuring the dielectric loss tangent and the bulk dielectric loss tangent, as well as the methods for controlling them, are as described above.
• the difference (the dielectric loss tangent - the bulk dielectric loss tangent) is preferably -0.00002 or less, more preferably -0.00003 or less, even more preferably -0.00004 or less, even more preferably -0.00005 or less, even more preferably -0.00006 or less or -0.00007 or less, and particularly preferably -0.00008 or less.
• the dielectric loss tangent of the glass cloth may be greater than -0.0002.
• the glass yarn may be composed of a plurality of glass filaments.
• the glass yarn may be woven as a warp yarn and a weft yarn to produce a glass cloth.
• the average filament diameter of the glass filaments is preferably 2.5 to 9.0 ⁇ m, more preferably 2.5 to 7.5 ⁇ m, even more preferably 3.5 to 7.0 ⁇ m, still more preferably 3.5 to 6.0 ⁇ m, and particularly preferably 3.5 to 5.0 ⁇ m.
• the weight of the glass cloth is preferably 8 to 250 g/m 2 , more preferably 8 to 100 g/m 2 , still more preferably 8 to 80 g/m 2 , and particularly preferably 8 to 50 g/m 2 .
• Glass type glass cloth used in prepregs (laminates) is usually a glass raw material called E-glass (alkali-free glass).
• glass raw materials such as L-glass, NE-glass, D-glass, L2-glass, T-glass, silica glass, and quartz glass may be used.
• glass raw materials such as L-glass, L2-glass, silica glass, and quartz glass are preferably used, and among them, silica glass and quartz glass are particularly preferred.
• glass raw materials such as S-glass, T-glass, silica glass, and quartz glass are preferably used, and among them, silica glass and quartz glass are particularly preferred.
• the silicon (Si) content of the glass yarns constituting the glass cloth is preferably 95.0 to 100 mass% or 99.0 to 100 mass%, more preferably 99.5 to 100 mass%, and even more preferably 99.9 to 100 mass%.
• a particularly preferred embodiment of the SiO2 composition amount of the glass yarns constituting the glass cloth is more than 99.9 mass%.
• weave structure examples of weave structures for the glass cloth include plain weave, sieve weave, satin weave, and twill weave, with plain weave structures being more preferred.
• the surface treatment liquid may contain a surface treatment agent.
• the surface treatment is performed, for example, by a method using a surface treatment liquid.
• a “strongly hydrophobic surface treatment agent (strongly hydrophobic silane coupling agent)” is defined as an agent in which, when an aqueous solution prepared by mixing a 0.3% by mass aqueous solution of acetic acid with a surface treatment agent (silane coupling agent) at a concentration of 0.8% by mass is stirred for 3 hours at room temperature of 25°C, the surface treatment agent (silane coupling agent) is not dissolved or uniformly dispersed in the aqueous solution; for example, the surface treatment agent (silane coupling agent) is separated in the aqueous solution as oil droplets and an oil film.
• the molecular weight of the surface treatment agent for example, the molecular weight of the silane coupling agent, is preferably 250 to 1,000, more preferably 270 to 800, still more preferably 300 to 750, and particularly preferably 350 to 700.
• the weighted average value of the molecular weights of the surface treatment agents, where the weight is the mass of each surface treatment agent, is within the above range, and it is more preferable that the molecular weights of all of the multiple surface treatment agents used are within the above range.
• the surface treatment agent preferably contains a silane coupling agent. That is, the glass threads (including glass filaments) constituting the glass cloth are preferably surface-treated with a silane coupling agent.
• the surface treatment agent is, for example, a compound represented by the following formula (1): X 3-n SiY n ...(1) (In the formula, each X is independent and may contain a different organic functional group, and is composed of a functional group having a total of two or more carbonyl groups and two or more unsaturated carbon-carbon double bonds in X; each Y is independently an alkoxy group; and n is an integer of 1 or more and 3 or less.)
• the difference between the dielectric loss tangent of the glass cloth and the dielectric loss tangent of the glass bulk (the above-mentioned dielectric loss tangent - the above-mentioned bulk dielectric loss tangent) is made to be less than 0.00000, and further, it becomes easy to suppress an increase in the dielectric loss tangent of the glass cloth over time.
• the silane coupling agent preferably contains at least one group selected from the group consisting of an epoxy group, an amino group, an acryloyl group, and a methacryloyl group in its molecule.
• the above-mentioned X contains at least one group selected from the group consisting of an epoxy group, an amino group, an aromatic vinyl group, an acryloyl group, and a methacryloyl group.
• the alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms (1, 2, 3, 4, or 5 carbon atoms) from the viewpoint of the stability of the surface treatment on the glass cloth.
• the silane coupling agent contained in the surface treatment agent may be one of the silane coupling agents represented by formula (1) above, or a combination of multiple silane coupling agents.
• two or more silane coupling agents having different X values may be mixed and used.
• silane coupling agent represented by the general formula (1) examples include: 4-(Trimethoxysilyl)phenyl 2-methyl-2-propenoate, 1-[2-(Trimethoxysilyl)ethyl]pentyl 2-methyl-2-propenoate, [4-[2-(Trimethoxysilyl)ethyl]phenyl]methyl 2-propenoate, N-2-Propen-1-yl-N-[3-(trimethoxysilyl)propyl]-2-oxiranemethanamine, 3-(Ethenyloxy)-2-[(trimethoxysilyl)oxy]propyl 2-propenoate, 6-[[[3-(Trimethoxysilyl)propyl]amino]carbonyl]-2-naphthalenyl 2-methyl-2-propenoate, 3-[2-(Trimethoxysilyl)ethyl]tricyclo[3.3.1.1 3,7 ]dec-1-yl 2-methyl-2-propenoate, 4
• the silane coupling agent that can be used can be appropriately adjusted depending on the dielectric loss tangent of the glass cloth before surface treatment, the matrix resin used in the resin substrate, etc.
• the silane coupling agent represented by the above formula (1) may be used in combination with a silane coupling agent other than that represented by the above formula (1).
• the average degree of opening of the glass cloth is preferably 38% or more or more than 40%, more preferably more than 43%, still more preferably more than 46%, more than 50%, more than 53%, more than 56%, or more than 60%, and particularly preferably more than 65%.
• the average degree of opening of the glass cloth is 38% or more, it is easy to prevent air bubbles called voids from remaining in the bundle of glass yarns when a resin substrate is produced, and as a result, it is difficult for adverse effects to occur on solder heat resistance, insulation reliability, etc.
• the silane coupling agent represented by the formula (1) tends to have a relatively strong intermolecular force, and therefore tends to be less effective in impregnating the glass cloth with the matrix resin than silane coupling agents other than those represented by the formula (1). Therefore, in order to fully obtain the effect of improving the insulation reliability of the glass cloth surface-treated with the silane coupling agent represented by the formula (1), it is preferable that the average degree of opening is 38% or more, or exceeds 40%.
• the ignition loss value of the glass cloth is preferably 0.01 to 0.5 mass%, or 0.01 to 0.4 mass%, or 0.01 to 0.3 mass%, more preferably 0.02 to 0.25 mass%, even more preferably 0.03 to 0.22 mass%, even more preferably 0.03 to 0.17 mass%, and particularly preferably 0.04 to 0.15 mass%.
• the ignition loss value is 0.01 mass% or more, adhesion between the resin and the glass cloth in the obtained prepreg is easily ensured. In this case, heat resistance and insulation reliability are easily ensured when a printed wiring board is produced.
• the ignition loss value of the glass cloth is 0.5% by mass or less, it is easy to avoid a situation in which a surface treatment agent (or its residue) that is physically attached to the glass cloth surface without forming a chemical bond with the glass cloth surface, a surface treatment agent (or its residue) that cannot be removed from the glass cloth surface by washing with water, and/or modified products thereof are present in large amounts on the glass cloth surface, which makes it easy to achieve a low dielectric loss tangent of the glass cloth.
• White spots on glass cloth White stains (white spots) may be observed on the surface of the surface-treated glass cloth. These white spots tend to repel the matrix resin used in preparing the prepreg, which may result in poor appearance of the resulting prepreg. It has been previously believed that the cause of these white spots is unknown.
• the present inventors have clarified that one of the white spots is an aggregate of a highly hydrophobic surface treatment agent (for example, a highly hydrophobic silane coupling agent) or a modified product thereof.
• a highly hydrophobic surface treatment agent for example, a highly hydrophobic silane coupling agent
• the silane coupling agent represented by the above formula (1) is relatively highly hydrophobic, and therefore tends to easily generate aggregates, and that when the solvent in the surface treatment solution contains water, the frequency of white spots occurring on the glass cloth after surface treatment tends to increase (for example, 10.0 spots/ m2 or more).
• the frequency of white spots in the glass cloth is preferably 7.0 spots/ m2 or less, more preferably 4.0 spots/ m2 or less, even more preferably 2.0 spots/ m2 or less or 0.1 spots/ m2 or less, and particularly preferably 0.05 spots/ m2 or less. This makes it easy to realize a prepreg with excellent appearance.
• the frequency of white spots in the glass cloth may be more than 0 spots/ m2 .
• One aspect of this embodiment is a manufacturing method for manufacturing the glass cloth of this embodiment.
• the manufacturing method of this embodiment is as follows: a weaving process for weaving glass yarn to obtain glass cloth; a surface treatment step of deoiling the glass filaments and then surface treating the glass filaments with a surface treatment solution, The dielectric loss tangent at 10 GHz of the glass cloth after the surface treatment is lower than the dielectric loss tangent at 10 GHz of the glass cloth before the surface treatment.
• the manufacturing method of this embodiment may optionally include the following steps: a step of heating the glass yarn to reduce the amount of fiber sizing agent adhering to the glass yarn (thermal deoiling step); A step of washing the glass yarn with water (finish washing step), and/or a step of opening the glass yarn (opening step).
• At least one of the surface treatment process, fiber-opening process, and finish-washing process may be performed on the glass yarn before the process of weaving the glass yarn to obtain glass cloth (weaving process), or on the glass cloth after the weaving process.
• the order of the thermal deoiling process, surface treatment process, fiber-opening process, and finish-washing process may be reversed. If the washing process is performed after the weaving process, the washing process can also serve as the fiber-opening process by using a high-pressure water spray, etc.
• the composition of the glass cloth usually does not change before and after fiber-opening.
• Heat deoiling process In this step, by heating the glass yarn, it is possible to reduce, and preferably remove, the fiber sizing agent (sizing agent), its residues, and modified products thereof that are arbitrarily attached to the glass yarn. By performing the thermal deoiling step, it is possible to form a surface treatment layer on the surface of the glass yarn (glass filament) after reducing organic substances that can increase the dielectric loss tangent, and therefore it is easy to produce a glass cloth with excellent dielectric properties.
• known means heating means, heating medium, heating mechanism, heating device, heating component, etc.
• One embodiment of the thermal deoiling step is, for example, A method of heating the glass cloth at a temperature of 600 to 1600°C. etc. are known.
• heating the glass cloth fabric, whose glass yarn has a softening point of 900°C or higher, in a temperature range of 600 to 1600°C makes it easier to minimize damage to the glass cloth and reduce the dielectric tangent of the glass cloth.
• the thermal deoiling temperature is preferably 700 to 1500°C, more preferably 800 to 1400°C, even more preferably 900 to 1300°C, and particularly preferably 1000 to 1200°C.
• a thermal deoiling temperature of 600°C or higher makes it easier to effectively remove sizing agents and the like adhering to the glass cloth green fabric, making it easier to produce glass cloth with excellent dielectric properties.
• a thermal deoiling temperature of 1600°C or lower makes it easier to suppress devitrification of the glass, and as a result, makes it easier to prevent a decrease in the strength of the glass cloth.
• the heating time is preferably 1 hour or less or 30 minutes or less, more preferably 15 minutes or less, and even more preferably 5 minutes or less. Heating the glass cloth at a high temperature for a sufficient time tends to induce a dehydration condensation reaction of the silanol groups on the glass surface. From the perspective of effectively removing sizing agents, etc., the heating time may be, for example, 1 second or more, 5 seconds or more, 10 seconds or more, or 15 seconds or more.
• thermal deoiling of glass cloth is carried out in a closed system
• the glass cloth can be transported, for example, by a combination of an unwinding mechanism and a winding mechanism.
• the glass cloth can be transported, for example, by a combination of an unwinding mechanism and a winding mechanism.
• the mode of the thermal deoiling step is not limited to the above.
• a method of heating in a vacuum or in a gas with a dew point of 15°C or less under conditions where the heating amount, expressed as a heating temperature (°C) of 100°C or more x heating time (h), is 450 (°C ⁇ h) or more (provided that the maximum heating temperature is 100 to 600°C); etc. are also known.
• the heating means may be, for example, a heating furnace, an electric heater, a burner, etc., and among these, a gas single radiant tube burner or an electric heater is preferred. A plurality of different heating means may be combined.
• a continuous method in which the glass cloth is heated by continuously passing it through a heating furnace is preferred over a batch method in which the glass cloth wound around a core is heated at a predetermined ambient temperature.
• RO reverse osmosis
• devitrification of the quartz glass may cause a decrease in the tensile strength of the glass cloth if the glass cloth is deoiled by heating at 700°C or higher.
• washing the glass cloth with water containing 20 ppm or less sodium ions before deoiling can easily reduce the amount of sodium ions on the glass surface.
• devitrification of the quartz glass can be easily prevented even when deoiled by heating at 700°C or higher. Maintaining the strength of the glass cloth after deoiling by heating helps prevent wrinkles and/or scratches on the glass cloth during the surface treatment process.
• the sodium ion content of the water used for washing may be 18 ppm or less, 15 ppm or less, 12 ppm or less, 10 ppm or less, or 7 ppm or less.
• a sodium ion content of 0 ppm is preferred, but it may exceed 0.
• the means for cleaning glass cloth to a sodium ion content of 20 ppm or less may be any known cleaning method, as long as it is capable of removing sodium ions from the glass surface.
• Possible methods include, for example, ultrasonic methods (e.g., methods using an ultrasonic vibrator), spraying (e.g., spraying using a high-pressure spray), and water vapor spraying.
• a preferred method involves immersing the glass cloth in a water tank containing cleaning water (water with a sodium ion content of 20 ppm or less), removing excess cleaning water with a squeeze roller or the like, and then drying the glass cloth.
• the immersion time may be, for example, 2 seconds or more, 5 seconds or more, 10 seconds or more, 15 seconds or more, or 120 seconds or less, 90 seconds or less, 60 seconds or less, or 45 seconds or less.
• Water with a sodium ion content of 20 ppm or less can be produced by any known production method. For example, methods such as filtration using an RO membrane or deionization using an ion exchange resin are possible. "Water with a sodium ion content of 20 ppm or less" may contain other liquid components (liquids other than water, etc.) as long as the effects of the present invention are not impaired.
• the surrounding environment As moisture-free as possible during the period from thermal deoiling to lowering the temperature of the glass cloth surface to 100°C or less, that is, to reduce the surrounding moisture during thermal deoiling.
• methods for reducing the surrounding moisture during thermal deoiling include: A method of introducing dry air into a heating furnace, a method of creating a vacuum inside the furnace, a method of introducing an inert gas such as nitrogen into the furnace, When the thermal deoiling treatment is carried out while the glass cloth is being conveyed, it is preferable to introduce an inert gas such as nitrogen into the furnace.
• the glass filaments are treated with a surface treatment solution containing a surface treatment agent having a molecular weight of 200 or more.
• a method for treating the glass filament with a surface treatment liquid for example, a method for applying a surface treatment liquid to the glass filament
• a method in which a glass cloth is transported while being immersed in a surface treatment solution stored in a bath hereinafter referred to as the "immersion method”
• the immersion time of the glass cloth in the surface treatment solution is preferably selected to be 0.5 seconds or more and 1 minute or less.
• the glass fiber is surface-treated using a predetermined surface treatment agent, particularly a predetermined silane coupling agent (in one embodiment, a silane coupling agent that is advantageous in terms of reducing the dielectric tangent of the glass cloth).
• a predetermined silane coupling agent in one embodiment, a silane coupling agent that is advantageous in terms of reducing the dielectric tangent of the glass cloth.
• the silane coupling agent used in the method of this embodiment is more hydrophobic than general silane coupling agents.
• the present inventors have found that in a given surface treatment solution, it is possible to suppress white spots on glass cloth by taking the following measures (A) to (C), for example: (A) adding a solvent (for example, a weakly acidic aqueous solution as a mother liquor) to the surface treatment agent; (B) controlling the temperature and/or pH of the surface treatment solution during the surface treatment; (C) Filtering the surface treatment solution during the surface treatment.
• a solvent for example, a weakly acidic aqueous solution as a mother liquor
• a surfactant and a small amount of solvent for hydrolyzing the silane coupling agent for example, a 60% aqueous acetic acid solution
• the solvent added to the pre-solution is added to hydrolyze the alkoxide groups of the silane coupling agent, and the amount of solvent added is preferably adjusted depending on the amount of hydrolysis. Then, an aqueous solution adjusted to a pH of 3 to 4 (also referred to as the "mother liquor" in this disclosure) is added little by little to the pre-solution while stirring, thereby uniformly dispersing the surface treatment agent in the aqueous solution. In this case, it is easy to suppress agglomerations in the surface treatment solution.
• the content of the silane coupling agent in the surface treatment solution is preferably in the range of 0.01 to 2.0 mass%, more preferably 0.01 to 1.8 mass%, even more preferably 0.02 to 1.5 mass%, even more preferably 0.02 to 1.3 mass%, and particularly preferably 0.02 to 1.0 mass%. If the content of the silane coupling agent exceeds 2.0 mass%, the amount of silane coupling agent attached to the glass cloth becomes too large, which tends to increase the dielectric loss tangent of the glass cloth. Furthermore, the relatively large number of silanol groups not bonded to the glass cloth makes it more likely to adsorb moisture from the air, which results in an increase in the dielectric loss tangent of the glass cloth over time.
• the content of the silane coupling agent is below 0.01 mass%, the amount of silane coupling agent attached to the glass cloth is too small, which makes it difficult for the reaction between the silane coupling agent and the matrix resin to proceed sufficiently, which can adversely affect the solder heat resistance of the substrate.
• the surfactant composition and amount can be changed as appropriate depending on the type and amount of the surface treatment agent, and any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants may be used. Different types of surfactants may also be used in combination.
• the amount of surfactant is preferably 0.2 to 10% by mass, more preferably 0.4 to 9% by mass, even more preferably 0.6 to 8% by mass, and particularly preferably 1 to 6% by mass, relative to the surface treatment agent (e.g., silane coupling agent).
• the surface treatment agent e.g., silane coupling agent
• Nonionic surfactants include glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene glycols, fatty acid polyethylene glycols, fatty acid polyoxyethylene sorbitan, and fatty acid alkanolamides.
• Anionic surfactants include fatty acid monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acylsarcosinates, N-acylglutamates, dialkyl sulfosuccinates, alkane sulfonates, alpha-olefin sulfonates, linear alkylbenzene sulfonates, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, alkylnaphthalene sulfonates, N-methyl-N-acyltaurates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fat and oil sulfate esters, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, etc.
• cationic surfactants include monoalkylamine salts, dialkylamine salts, trialkylamine salts, alkyltrimethylammonium chloride, and alkylbenzalkonium chloride.
• Amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyl betaine, fatty acid amidopropyl betaine, alkyldiethylenetriaminoacetic acid, and alkylamine oxide.
• the temperature of the surface treatment liquid is preferably controlled at 10 to 30°C, more preferably at 13 to 27°C, even more preferably at 15 to 25°C, and particularly preferably at 17 to 23°C during the surface treatment.
• the pH of the surface treatment solution is preferably controlled to between 2.5 and 5.5, more preferably between 2.8 and 5.2, and even more preferably between 3.0 and 5.0.
• One method for controlling the pH within a predetermined range is, for example, bubbling carbon dioxide into the surface treatment solution.
• either one of these controls may be performed, or both may be performed. From the perspective of effectively suppressing agglomerations in the surface treatment liquid, it is preferable to perform both the temperature control of the surface treatment liquid and the pH control of the surface treatment liquid.
• temperature control of the surface treatment liquid is a concept that includes not only an operation of increasing and/or decreasing the temperature of the surface treatment liquid, but also an operation of maintaining the temperature of the surface treatment liquid at a predetermined value, and an operation of detecting the temperature of the surface treatment liquid to confirm whether the temperature is within a predetermined range.
• pH control of the surface treatment solution includes not only an operation for increasing and/or decreasing the pH of the surface treatment solution, but also an operation for maintaining the pH of the surface treatment solution at a predetermined value, and an operation for detecting the pH of the surface treatment solution to determine whether the pH is within a predetermined range.
• (C) Filtration of the surface treatment liquid From the viewpoint of reliably collecting aggregates in the surface treatment liquid, it is preferable to filter the surface treatment liquid during the surface treatment. In this case, it is preferable to collect aggregates that may occur in the surface treatment liquid by filtration while circulating the surface treatment liquid.
• multiple stages of filtration In order to increase the efficiency of collecting agglomerates, it is preferable to use multiple stages of filtration. For example, two-stage filtration is preferable, in which agglomerates are first removed using a filter with relatively coarse mesh, and then the surface treatment liquid is filtered again using a filter with finer mesh than the primary filter.
• Such multiple-stage filtration makes it easier to prevent filter clogging, and as a result, makes it easier to avoid interruptions to the glass cloth production process.
• the surface treatment process is a step of applying a surface treatment liquid to the glass fiber and then drying the solvent contained in the surface treatment liquid (drying step); It may further include: The drying step makes it easy to fix the surface treatment agent to the surface of the glass yarn (surface of the glass filaments), and in particular makes it easy to fix the surface treatment agent to the surface of each individual glass yarn (surface of each individual glass filament).
• methods for drying the solvent include known methods such as drying by heating, specifically, methods of heating and drying by hot air, electromagnetic waves, etc.
• the drying temperature is preferably 80°C or higher, more preferably 90°C or higher, from the viewpoint of ensuring sufficient reaction between the surface treatment agent and the glass. Furthermore, the drying temperature is preferably 300°C or lower, more preferably 180°C or lower, from the viewpoint of preventing deterioration of the organic functional groups contained in the surface treatment agent.
• the manufacturing method of this embodiment preferably includes a fiber-opening step after the surface treatment step.
• the opening method in the opening step include opening the glass cloth with spray water (high-pressure water opening), a vibro washer, ultrasonic water, a mangle, or the like.
• spray water high-pressure water opening
• a vibro washer By reducing the tension applied to the glass cloth during this opening process, the width of the glass yarns can be easily increased and the surface treatment agent that has not chemically bonded to the glass surface can be easily removed to some extent.
• it is preferable to take measures such as reducing the friction of contacting members when weaving the glass yarns, optimizing the sizing agent and increasing the amount of adhesion.
• the washing step is preferably a method capable of reducing the residue of the surface treatment agent that has not formed a chemical bond with the surface of the glass filaments, modified substances, etc., such as a method of washing the glass filaments with an organic solvent.
• a glass raw material with a high silicon (Si) content such as quartz glass, it becomes easy to adjust the difference between the dielectric loss tangent and the bulk dielectric loss tangent of the obtained glass cloth to fall within a predetermined range.
• washing with a highly hydrophobic organic solvent is preferred in order to reduce the above-mentioned residues that are difficult to reduce with water, and washing with an organic solvent that has a high affinity for silane coupling agent residues having hydroxyl groups is also preferred.
• the washing method include known methods such as immersion and shower spraying, and washing may be performed while heating or cooling as necessary.
• Suitable organic solvents include: saturated chain aliphatic hydrocarbons such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, 2,2,4-trimethylpentane (isooctane), n-nonane, i-nonane, n-decane, i-decane, and 2,2,4,6,6-pentamethylheptane (isododecane); saturated cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethyl
• aromatic hydrocarbons, alcohols, or ketones are preferred, and methanol is more preferred, from the viewpoint of making it easier to adjust the difference between the dielectric loss tangent and bulk dielectric loss tangent of the resulting glass cloth to within a specified range.
• the manufacturing method of this embodiment preferably includes a step of drying the washed glass cloth (post-washing drying step) in order to reduce the amount of organic solvent used after washing.
• the organic solvent used for washing has a boiling point of 120°C or less.
• Known methods such as heat drying and air drying can be used to dry the organic solvent.
• the drying temperature is preferably above the boiling point of the washing solvent, and is preferably below 180°C to prevent deterioration of the silane coupling agent.
• the manufacturing method of this embodiment may optionally include other steps in addition to the steps described above.
• the other steps include, for example, a step of processing the glass cloth into slits (slit processing step).
• the prepreg of this embodiment contains glass cloth, a matrix resin, and an inorganic filler.
• the prepreg of this embodiment can be made by using the glass cloth of this embodiment as the glass cloth. This provides a prepreg with excellent properties (for example, a prepreg with few voids).
• thermosetting resin either a thermosetting resin or a thermoplastic resin can be used.
• Thermosetting resins and thermoplastic resins may be used in combination.
• thermosetting resins include: a) an epoxy resin obtained by reacting a compound having an epoxy group with a compound having at least one group reactive with the epoxy group, such as an amino group, a phenol group, an acid anhydride group, a hydrazide group, an isocyanate group, a cyanate group, or a hydroxyl group, without a catalyst or by reacting with the addition of a catalyst having a reaction catalytic ability, such as an imidazole compound, a tertiary amine compound, a urea compound, or a phosphorus compound, followed by curing; b) a radical polymerization type curable resin obtained by curing a compound having at least one of an allyl group, a methacryl group, and an acrylic group using a thermal decomposition type catalyst or a photodecomposition type catalyst as a reaction initiator; c) a maleimide triazine resin obtained by reacting a compound having a cyanate group with a compound having a
• thermoplastic resins include polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyarylate, aromatic polyamide, polyether ether ketone, thermoplastic polyimide, insoluble polyimide, polyamide imide, LCP, polyester, and fluororesin.
• the prepreg may contain an inorganic filler.
• inorganic fillers include aluminum hydroxide, zirconium oxide, calcium carbonate, alumina, mica, aluminum carbonate, magnesium silicate, aluminum silicate, silica, talc, short glass fibers, aluminum borate, and silicon carbide.
• the inorganic filler may be used in combination with the thermosetting resin.
• the printed wiring board of this embodiment includes a prepreg.
• the printed wiring board of this embodiment includes the prepreg of this embodiment as the prepreg. This provides a printed wiring board with excellent properties (for example, a printed wiring board with excellent insulation reliability).
• the integrated circuit of this embodiment includes the printed wiring board of this embodiment.
• the electronic device of this embodiment includes the printed wiring board of this embodiment. These provide an integrated circuit and electronic device with various excellent characteristics.
• JIS R 3420 In accordance with 7.10 of JIS R 3420, a micrometer was used to gently rotate the spindle, bringing it into light contact parallel to the measurement surface, and the scale was read after the ratchet made three clicks. JIS R 3420 also specifies general test methods for long glass fibers and products such as glass cloth made from long glass fibers.
• the glass cloth was cut to a predetermined size to obtain a sample.
• the mass of the sample was divided by the area of the sample to determine the basis weight.
• the glass cloth was cut to a size of 10 cm x 10 cm to obtain a sample, and the mass was measured to determine the basis weight (g/ m2 ).
• the dielectric loss tangent of each glass cloth was measured in accordance with IEC 62562. Specifically, glass cloth samples were sampled to the size required for measurement with each split cylinder resonator and stored in a constant temperature and humidity oven at 23°C and 50% RH for 8 hours to condition the humidity. The dielectric properties at 10 GHz were then measured using a split cylinder resonator (manufactured by EM Lab) and an impedance analyzer (manufactured by Agilent Technologies). The measurement was performed five times for each sample, and the average value was calculated. The thickness of each sample was the equivalent thickness. IEC 62562 specifies a method for measuring the dielectric properties in the microwave band of fine ceramic materials for dielectric substrates, primarily used in microwave circuits.
• a glass plate having a thickness of 300 ⁇ m and the same type and composition as each glass cloth for which the dielectric loss tangent was measured was prepared. The thickness obtained from the thickness measurement of the glass plate was used to measure the bulk dielectric loss tangent at 10 GHz in the same manner as in the measurement of the dielectric loss tangent.
• Warp opening rate (%) [warp width ( ⁇ m) / ⁇ number of warp filaments ⁇ warp filament diameter ( ⁇ m) ⁇ ] ⁇ 100 It was calculated by:
• the opening degree of the weft yarn of the glass cloth was calculated using the following formula:
• Weft opening rate (%) [weft width ( ⁇ m) / ⁇ number of weft filaments ⁇ weft filament diameter ( ⁇ m) ⁇ ] ⁇ 100 It was calculated by:
• Average opening rate (%) ⁇ opening rate of warp yarn (%) + open rate of weft yarn (%) ⁇ / 2
• the average degree of opening was calculated by the above.
• the number of filaments in each of the warp and weft yarns was determined by observing a cross-sectional image of the glass yarn. Specifically, a cross-sectional image of the glass yarn as the warp yarn (or the weft yarn) was obtained, and the number of filaments in the warp yarn (or the weft yarn) was measured in the cross-sectional image. Similarly, image acquisition of the glass yarn and measurement of the number of filaments were repeated, and the average value of the five measurements obtained was used as the number of filaments in the warp (or weft).
• warp width and weft width were determined by the following method. First, five glass cloth test pieces each measuring 70 mm in the warp direction and 70 mm in the weft direction were cut out from the glass cloth. Each cut specimen was observed vertically using a macroscope at 100x magnification. For each specimen, the widths of 250 warp yarns (or weft yarns) were randomly measured, and the average value of the widths of the 250 warp yarns (or weft yarns) was calculated. The average value was used as the warp width (or weft width).
• the warp and weft yarns were composed of glass yarns with a SiO2 composition of more than 99.9% by mass. Specifically, the warp and weft yarns were glass yarns with an average filament diameter of 5.0 ⁇ m, 100 filaments, and a twist of 1.0Z. Then, using an air jet loom, 2000 m of glass cloth was woven with a plain weave structure, a warp density of 66/25 mm and a weft density of 68/25 mm, and a cloth width of 1300 mm. The bulk dielectric loss tangent at 10 GHz of the glass constituting the glass yarns was 0.00020.
• the warp and weft yarns were composed of glass yarns with a SiO2 composition of more than 99.9% by mass. Specifically, the warp and weft yarns were glass yarns with an average filament diameter of 5.0 ⁇ m, 200 filaments, and a twist of 1.0Z. Then, using an air jet loom, 2000 m of glass cloth was woven with a plain weave structure, a warp density of 54/25 mm, a weft density of 54/25 mm, and a cloth width of 1300 mm. The bulk dielectric loss tangent at 10 GHz of the glass constituting the glass yarns was 0.00020.
• the warp and weft yarns were composed of glass yarns with a SiO2 composition of more than 99.9% by mass. Specifically, the warp and weft yarns were glass yarns with an average filament diameter of 4.0 ⁇ m, 50 filaments, and a twist of 1.0Z. Then, using an air jet loom, 2000 m of glass cloth was woven with a plain weave structure, a warp density of 95/25 mm and a weft density of 95/25 mm, and a cloth width of 1300 mm. The bulk dielectric loss tangent at 10 GHz of the glass constituting the glass yarns was 0.00020.
• the surface treatment solutions were prepared according to the following methods 1) to 5). 1) The silane coupling agent was weighed. 2) Methanol in an amount equal to the amount weighed out in 1) above was mixed with the silane coupling agent weighed out in 1) above to prepare a silane coupling agent solution. 3) The silane coupling agent solution was mixed with 0.8% by mass of polyoxyethylene alkyl ether relative to the silane coupling agent and stirred. After stirring for 1 minute, 20% by mass of acetic acid aqueous solution (concentration 60% by mass) relative to the silane coupling agent was added to the silane coupling agent solution. This hydrolyzed the silane coupling agent.
• the silane coupling agent solution (pre-solution) obtained in 3) above was stirred for 15 minutes at room temperature of 20 to 25°C. At this time, the mother liquor was added dropwise to the stirred silane coupling agent solution, thereby dispersing the silane coupling agent.
• the amount of mother liquor added (dropping rate) was set so that the entire amount of mother liquor was added dropwise within 10 minutes. 5) After step 4), the silane coupling agent solution was stirred at room temperature of 20 to 25° C. for 2 hours to obtain a surface treatment liquid.
• the "solvent" in the “step of adding a solvent to a surface treatment agent to prepare a surface treatment liquid” of the present disclosure is the mother liquor described above.
• an example of the mother liquor is a weakly acidic aqueous solution with a pH of 3 to 4, which is added for the purpose of dispersing the silane coupling agent after hydrolysis.
• Example 1 The glass cloth P was washed with ion-exchanged water and then dried. This removed alkali metal ions and the like adhering to the surface of the glass cloth. Thereafter, the glass cloth was heated and deoiled for 5 minutes while being conveyed in a furnace adjusted to a set temperature of 1000°C (thermal deoiling step). The furnace was adjusted to a nitrogen atmosphere during the thermal deoiling.
• the glass cloth which had been heated and deoiled, was immersed in the resulting surface treatment solution. Then, excess surface treatment solution was squeezed out using an NBR rubber roll at a pressure of 0.3 MPa. The glass cloth was then heated and dried at 130°C for 1 minute, thereby adhering the silane coupling agent to the surface of the glass cloth.
• temperature control e.g., cooling
• carbon dioxide was bubbled into the surface treatment solution to keep the pH of the surface treatment solution in the range of 3.0 to 4.0 while the glass cloth was being surface treated.
• the surface treatment solution used for the surface treatment of the glass cloth was filtered using an HDCII filter (manufactured by Nippon Pall Corporation). That is, the surface treatment solution was first passed through a filter with a mesh size of 10 ⁇ m, and then passed through a filter with a mesh size of 4.5 ⁇ m. This allowed for the capture of any aggregates that may be present in the surface treatment solution.
• the filtered surface treatment solution was used for the surface treatment of the glass cloth.
• the surface-treated glass cloth was subjected to a pressure of 3.0 kg/ cm2 using a spray nozzle, thereby high-pressure opening.
• ultrasonic waves with a frequency of 25 kHz and an output of 0.50 W/ cm2 were applied in water, further opening the glass cloth while reducing excess silane coupling agent physically attached to the glass cloth.
• the glass cloth was then dried by heating at 130°C for 1 minute. As a result of the above, 2000 m of surface-treated glass cloth was obtained.
• Example 7 A glass cloth of 2000 m was obtained in the same manner as in Example 1, except that the glass cloth Q was used instead of the glass cloth P.
• Example 8 A glass cloth of 2000 m was obtained in the same manner as in Example 1, except that the glass cloth R was used instead of the glass cloth P.
• Example 9 A glass cloth of 2000 m was obtained in the same manner as in Example 3, except that the surface treatment was carried out without filtering the surface treatment solution.
• Example 10 A glass cloth of 2000 m was obtained in the same manner as in Example 1, except that the concentrations of the surface treatment liquid were adjusted to a total of 0.4 mass% with 0.2 mass% of silane coupling agent A and 0.2 mass% of silane coupling agent B, and that the fiber-opening was not performed using a spray nozzle, but instead was performed using ultrasonic waves at an output of 0.20 W/ cm2 .
• Example 11 A glass cloth of 2000 m was obtained in the same manner as in Example 3, except that the surface treatment solution was not cooled even when the temperature of the surface treatment solution exceeded 23°C, and that carbon dioxide bubbling was not performed even when the pH exceeded 4.0.
• Example 1 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 1, except that the concentration of the surface treatment solution was adjusted to 0.9 mass % and the thermal deoiling temperature was changed to 700°C.
• Example 2 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 1, except that the concentration of the surface treatment solution was adjusted to 2.5 mass %.
• Example 3 A 2000 m glass cloth was obtained in the same manner as in Example 1, except that a surface treatment liquid was prepared by dropping a silane coupling agent solution into a mother liquid of an aqueous acetic acid solution under stirring, that the surface treatment liquid was not filtered but the surface treatment of the glass cloth was carried out, that the surface treatment liquid was not cooled even when the temperature of the surface treatment liquid exceeded 23°C, and that carbon dioxide bubbling was not carried out even when the pH exceeded 4.0.
• Figure 1 shows photographs for explaining the "white spot" in this example.
• Figure 1(a) shows a photograph of a portion without a white spot
• Figure 1(b) shows a photograph of a portion with a white spot P.
• a defect in which a white outline is observed upon irradiation with UV light and the area enclosed by the outline (the area including the outline) is 0.8 cm2 or more is defined as a "white spot.”
• the outline is, for example, circular.
• the area enclosed by the contour line was calculated using known image analysis software.
• Prepreg manufacturing method 1 polyphenylene ether resin was used as a raw material. That is, 45 parts by mass of polyphenylene ether (Noryl SA9000 manufactured by SABIC), 10 parts by mass of triallyl isocyanurate, 45 parts by mass of toluene, and 0.6 parts by mass of 1,3-di(tert-butylisopropylbenzene) were added to a stainless steel container and stirred at room temperature for 1 hour to prepare a varnish. The glass cloths obtained in Examples 1 to 4, 6 to 11 and Comparative Examples 1 to 3 were impregnated with the prepared varnish and then dried at 130° C. for 1 minute to obtain prepregs.
• polyphenylene ether Noryl SA9000 manufactured by SABIC
• triallyl isocyanurate 45 parts by mass of toluene
• 1,3-di(tert-butylisopropylbenzene) 1,3-di(tert-butylisopropylbenzene)
• a varnish was prepared by blending 80 parts by mass of low-brominated bisphenol A epoxy resin, 20 parts by mass of cresol novolac epoxy resin, 2 parts by mass of dicyandiamide, 0.2 parts by mass of 2-ethyl-4-methylimidazole, and 100 parts by mass of 2-methoxyethanol.
• the glass cloths obtained in Examples 4 and 5 were impregnated with the prepared varnish and then dried at 130° C. for 7 minutes to obtain prepregs.
• the resulting prepreg was sampled to a size of 20 cm x 20 cm. Eight of the resulting samples were stacked, and 12 ⁇ m thick copper foil was placed on the top and bottom layers. The sample was then heated and pressed at 195°C and 40 kg/ cm2 for 120 minutes to produce a resin substrate.
• Laminate samples that showed blistering due to delamination at the glass cloth/resin interface were rated as "failed,” and the number of such "failed" laminate samples was recorded. The fewer the number of glass cloths listed in the table, the more excellent the heat resistance.
• a glass cloth was provided that was capable of achieving excellent dielectric properties, suppressing an increase in the dielectric loss tangent over time, and achieving excellent solder heat resistance for resin substrates made using the glass cloth.
• Comparative Examples 1 and 2 were unable to suppress an increase in the dielectric loss tangent over time
• Comparative Example 3 was unable to achieve excellent solder heat resistance.
• the present invention can be used in fields related to glass cloth, printed wiring boards (especially printed wiring boards for high-speed communication), etc.

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