Classifications

• • 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
• • 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
  • 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
• • 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
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2101/00—Inorganic fibres
  • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
  • D10B2101/06—Glass
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/16—Physical properties antistatic; conductive
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/18—Physical properties including electronic components

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 in order to reduce the dielectric tangent of glass cloth, the amount of silanol groups on the glass surface is reduced by heating silica glass cloth at high temperatures. Furthermore, in order to extend the life of drills in the glass cloth drilling process, Patent Document 5 reports obtaining glass yarn by spinning glass fibers with a softening point of 1000 to 1600°C, and producing glass cloth using such glass yarn.
• an example of an embodiment of the present disclosure can provide a glass cloth that has excellent dielectric properties and also has excellent insulation reliability, in that the whitening distance of the resulting resin substrate is small.
• An example of an aspect of the present disclosure is as follows.
• a glass cloth made by weaving glass yarn, the glass cloth is surface-treated with a surface treatment agent,
• the following formula A is calculated from the total carbon amount of the glass cloth and the peak height derived from the carbonyl group measured by Fourier transform infrared spectroscopy:
• Formula A peak height derived from carbonyl groups/total carbon content of the glass cloth is 10 or more, A glass cloth having 10 or less white spots per square meter.
• a glass cloth made by weaving glass yarn, The glass cloth is surface-treated with a surface treatment agent, The following formula B is calculated from the ignition loss value of the glass cloth and the peak height derived from the carbonyl group measured by Fourier transform infrared spectroscopy: Formula B peak height derived from carbonyl groups / ignition loss value of glass cloth is 11 or more, A glass cloth having 10 or less white spots per square meter. [3] 3. The glass cloth according to item 1 or 2, wherein the silicon (Si) content in the glass yarn is 95.0 to 100% by mass in terms of silicon dioxide (SiO 2 ). [4] 4. The glass cloth according to any one of items 1 to 3, having a dielectric loss tangent at 10 GHz of 0.002 or less. [5] 5.
• the surface treatment agent comprises a silane coupling agent.
• the surface treatment agent is 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.) 7.
• Item 9 The glass cloth according to any one of items 1 to 8, wherein the ignition loss value of the glass cloth is in the range of 0.01 to 0.5 mass%.
• an 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%.
• Item 12. A prepreg comprising the glass cloth according to any one of items 1 to 11 and a matrix resin.
• Item 13 A printed wiring board comprising the prepreg according to item 12.
• Item 14 An integrated circuit comprising the printed wiring board according to item 13.
• Item 14 An electronic device comprising the printed wiring board according to item 13.
• the surface treatment step includes: a step of adding a solvent to the surface treatment agent to prepare the surface treatment liquid; controlling the temperature of the surface treatment solution; controlling the pH of the surface treatment solution; and filtering the surface treatment solution;
• the surface treatment step includes: The method includes a step of surface-treating the deoiled glass fiber with a surface treatment agent,
• the surface treatment agent has 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
• the method for producing glass cloth according to item 15, comprising the step of: [18]
• the surface treatment step includes: controlling the temperature and pH of the surface treatment solution; Item 18.
• Item 19 The method for producing a glass cloth according to any one of Items 16 to 18, further comprising a step of subjecting the glass yarns to an opening treatment after the surface treatment step.
• 20. The method for producing a glass cloth according to any one of items 16 to 19, further comprising inspecting the glass cloth for white spots. [21] 21.
• the present disclosure it is possible to provide a glass cloth that can realize excellent dielectric properties and excellent insulation reliability, and further, can obtain a resin substrate with a small whitening distance. 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.
• FIG. 4 is a diagram for explaining a calibration curve in this embodiment.
• 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 carbon content of the glass cloth is calculated from the total carbon content and the peak height derived from the carbonyl group measured by Fourier transform infrared spectroscopy using the following formula A:
• Formula A peak height derived from carbonyl groups/total carbon content of the glass cloth is 10 or more,
• the number of white spots is 10 or less per square meter (for example, 10.0 or less per square meter).
• the glass cloth is surface treated with a surface treatment agent.
• the glass cloth of this embodiment is suitable as a material for producing prepregs, printed wiring boards, integrated circuits, electronic devices, etc.
• the glass cloth of this embodiment is surface-treated with a surface treatment agent.
• a surface-treated glass cloth has a surface treatment agent attached to its surface.
• a surface treatment agent is attached to the surface of a glass cloth, this corresponds to "surface-treated with a surface treatment agent" in the present disclosure.
• the surface of the glass cloth includes “the surface of the glass yarn that constitutes the glass cloth.” Specific examples of the surface treatment, such as a method for detecting a surface treatment agent, types of surface treatment agents, and surface treatment techniques, will be described later.
• the results may vary due to factors such as the sensitivity of the light-receiving element and measurement errors.
• Total carbon content of glass cloth The total carbon content of the glass cloth is measured by a method for measuring the amount of carbon dioxide generated when the glass cloth is pyrolyzed, specifically, by the method described in the Examples. Since the total carbon content tends to increase as the amount of surface treatment agent attached to the glass cloth increases, the measurement method of the present disclosure makes it easy to simply evaluate the amount of surface treatment agent attached to the glass cloth.
• the total carbon content of the glass cloth is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.6% by mass, more preferably 0.01 to 0.5% by mass, even more preferably 0.01 to 0.4% by mass, and particularly preferably 0.01 to 0.3% by mass, 0.02 to 0.20%, 0.03 to 0.15, or 0.03 to 0.10% by mass. If the total carbon content is less than 0.01% by mass, the amount of surface treatment agent adhered to the glass cloth is often insufficient, making insulation failure more likely. If the total carbon content of the glass cloth exceeds 0.8% by mass, the dielectric loss tangent of the glass cloth is often high, making it difficult to achieve a low dielectric loss tangent of the glass cloth.
• the glass cloth of this embodiment is The carbon content of the glass cloth is calculated from the total carbon content and the peak height derived from the carbonyl group measured by Fourier transform infrared spectroscopy using the following formula A:
• the value of formula A peak height derived from carbonyl groups/total carbon amount of the glass cloth is 10 or more.
• a value of 10 or more in formula A means that the proportion of highly reactive components (components having carbonyl groups) in the surface treatment agent adhered to the glass cloth is high.
• one of the ideas of the present inventors is to focus on the "peak height derived from carbonyl groups” and the “total carbon content of the glass cloth” and to define the ratio between them (peak height derived from carbonyl groups/total carbon content of the glass cloth).
• a glass cloth having a high value of 10 or more in the formula A can be specified. According to this embodiment, since the value of formula A is high, it is possible to provide a glass cloth that can give a resin substrate with a small whitening distance, and also to provide a glass cloth that exhibits excellent dielectric properties and insulation reliability.
• the value of Formula A is 10 or more (e.g., 10.0 or more), preferably greater than 10 (e.g., greater than 10.0), preferably 11 or more (e.g., 11.0 or more), more preferably 12 or more (e.g., 12.0 or more), even more preferably 13 or more (e.g., 13.0 or more), even more preferably 15 (e.g., 15.0 or more), and particularly preferably 19 or more (e.g., 19.0 or more).
• a value of Formula A of 10 or more ensures adhesion between the glass cloth and the matrix resin, thereby reducing the whitening distance in the resulting resin substrate.
• the value of Formula A may be 60 or less (e.g., 60.0 or less).
• the ignition loss value of the glass cloth is measured by a method of thermally deoiling the glass cloth (surface-treated glass cloth), specifically, by the method described in the Examples. Since the ignition loss value tends to increase as the amount of surface treatment agent attached to the glass cloth increases, the measurement method of the present disclosure makes it easy to simply evaluate the amount of surface treatment agent attached to the glass cloth.
• 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%. If the ignition loss value is 0.01 mass% or more, the adhesion between the resin and the glass cloth in the resulting prepreg is likely to be good. In this case, when a printed wiring board is produced, heat resistance and insulation reliability are likely to be ensured.
• the ignition loss value of the glass cloth is 0.5 mass% or less, it is likely to avoid a situation in which a large amount of surface treatment agent (or its residue) physically adhered to the glass cloth surface without forming a chemical bond with it, a surface treatment agent (or its residue) that cannot be removed from the glass cloth surface by water washing, and/or modified products thereof, is present on the glass cloth surface. In this case, it is easy to achieve a low dielectric tangent for the glass cloth.
• a value of 11 or more in formula B means that the proportion of highly reactive components (components having carbonyl groups) in the surface treatment agent adhered to the glass cloth is high.
• one of the ideas of the present inventors is to focus on the "peak height derived from carbonyl groups” and the “ignition loss value of glass cloth” and to define the ratio between them (peak height derived from carbonyl groups/ignition loss value of glass cloth).
• a glass cloth having a high value of 11 or more in the formula B is specified. According to this embodiment, since the value of formula B is high, it is possible to provide a glass cloth that can give a resin substrate with a small whitening distance, and also to provide a glass cloth that exhibits excellent dielectric properties and insulation reliability.
• the value of Formula B is 11 or more (e.g., 11.0 or more), preferably greater than 11 (e.g., greater than 11.0), preferably 12 or more (e.g., 12.0 or more), more preferably 13 or more (e.g., 13.0 or more), even more preferably 14 or more (e.g., 14.0 or more), and particularly preferably 15 or more (e.g., 15.0 or more).
• a value of Formula B of 11 or more ensures adhesion between the glass cloth and the matrix resin, thereby reducing the whitening distance of the resulting resin substrate.
• the value of Formula B may be 60 or less (e.g., 60.0 or less).
• the glass cloth of this embodiment preferably has a dielectric loss tangent of 0.002 or less at 10 GHz.
• a glass cloth can provide a prepreg and a printed wiring board that can improve the 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 or less, or 0.0002 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 less. This makes it easier to achieve the effects of the present disclosure.
• the dielectric loss tangent and bulk dielectric loss tangent of the glass cloth are, for example, A process of removing deteriorated materials and residues present on the glass surface; can be controlled based on
• 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 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% by mass or 99.0 to 100% by mass, more preferably 99.5 to 100% by mass, and even more preferably 99.9 to 100% by mass.
• a particularly preferred embodiment of the SiO 2 content of the glass yarns constituting the glass cloth is greater than 99.9% by mass.
• a Si content of 95.0% by mass or greater facilitates ensuring the dielectric properties of the glass cloth and the dimensional stability of the laminate.
• the silicon content can be determined using known measurement techniques such as atomic absorption spectrometry, inductively coupled plasma (ICP), and optical emission spectroscopy. Specifically, using an apparatus such as ICP-AES or ICP-MS, a calibration curve can be prepared from a standard sample with a known content, and the silicon content of the sample to be measured can then be determined from the prepared calibration curve.
• 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.
• the surface treatment liquid may contain a surface treatment agent and a mother liquid (e.g., an aqueous acetic acid solution).
• concentration of the surface treatment agent e.g., a silane coupling agent
• the concentration of the surface treatment agent in the surface treatment liquid is preferably 0.1 to 2.0 mass%, more preferably 0.2 to 1.0 mass%.
• 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.) It is preferable that the compound contains a silane coupling agent represented by the formula:
• the unsaturated carbon-carbon double bond is preferably a bond derived from at least one of an acryloyl group and a methacryloyl group, from the viewpoint of easily improving the adhesion between the glass cloth and the matrix resin and easily reducing the whitening distance of the resin substrate.
• a particularly preferred embodiment of the unsaturated carbon-carbon double bond is a bond derived from 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: 2-Propenoic acid, 2-methyl-, (dimethoxysilylene)bis(oxy-2,1-ethanediyl) ester, 2-Propenoic acid, 2-methyl-, 1-[(trimethoxysilyl)methyl]-1,2-ethanediyl ester, 2-Propenoic acid, 2-methyl-, 2-[(trimethoxysilyl)methyl]-1,3-propanediyl ester, 1,1′-[2-[3-(Trimethoxysilyl)propoxy]-1,3-propanediyl] bis(2-methyl-2-propenoate), 1,1'-[2-[[(2-Methyl-1-oxo-2-propen-1-yl)oxy]methyl]-2-[[3-(triethoxysilyl)propoxy]methyl]-1,3-propanediyl] bis(2-methyl-2-propenoate), 1-[2-[(2-Met
• 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 molecular weight of the surface treatment agent for example, the molecular weight of the silane coupling agent, is preferably 200 to 900, more preferably 230 to 800, still more preferably 260 to 700, and particularly preferably 300 to 600. If the molecular weight is 900 or less, dispersibility in water tends to be good, and therefore, the occurrence of white spots on the glass cloth is easily suppressed.
• 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 average degree of opening of the glass cloth is, for example, 35% or more, and is preferably more than 40%, more preferably more than 43%, even 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 more than 35% or 40%, 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 less likely to have an adverse effect 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 35% or more, or exceeds 40%.
• 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 the preparation of the prepreg, which may result in poor appearance of the resulting prepreg and, in turn, poor solder heat resistance and insulation reliability in the resulting resin substrate. 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 surface treatment agent (for example, a silane coupling agent) or a modified product thereof.
• a surface treatment agent for example, a silane coupling agent
• the silane coupling agent represented by the above formula (1) has a relatively large molecular weight, and therefore 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 is greater than 0.
• 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 surface treatment step of treating the glass fiber with a surface treatment liquid containing a surface treatment agent having a molecular weight of 200 or more;
• the surface treatment process is a step of adding a solvent to a surface treatment agent to prepare a surface treatment liquid; adjusting the temperature of the surface treatment solution; adjusting the pH of the surface treatment solution; and filtering the surface treatment solution;
• the method includes at least one of the steps.
• 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 (cleaning step), and/or a step of opening the glass yarn (opening step).
• At least one of the surface treatment process, opening process, and cleaning 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, opening process, and cleaning process may be reversed. If the cleaning process is performed after the weaving process, the cleaning process can also serve as the opening process by using a high-pressure water spray, etc.
• the composition of the glass cloth usually does not change before and after 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 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.
• 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.
• the thermal deoiling temperature is 600°C or higher, sizing agents and the like adhering to the glass cloth fabric can be easily removed effectively, making it easier to produce glass cloth with excellent dielectric properties.
• the thermal deoiling temperature is 1600°C or lower, it makes it easier to suppress devitrification of the glass, and as a result, it makes it easier to prevent a decrease in the strength of the glass cloth.
• the heating time is preferably 30 minutes or less, more preferably 15 minutes or less, even more preferably 5 minutes or less, and particularly preferably 90 seconds or less. Because the heat treatment is performed at a high temperature, a heating time of 30 minutes or less tends to reduce damage to the glass cloth, making it easier to avoid problems such as partial holes being formed in the glass cloth or the glass cloth being cut during processing. 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
• the heating means may be such that the glass cloth is heated by bringing a member (contact member) heated to a predetermined temperature into contact with the glass cloth.
• the contact member is preferably capable of heating the glass cloth at high temperatures.
• the contact member is preferably in the form of a roll, as this allows for easier transport of the glass cloth.
• the contact member is preferably a roll that uses induction heating, which can be used in high-temperature regions and has relatively little temperature variation across the width. When the glass cloth is heated by the contact member, the temperature of the contact member and the surface temperature of the glass cloth are considered to be roughly equal.
• the method using the roll be equipped with a mechanism for removing adhering foreign matter, such as a blade.
• the means for applying the above to the glass cloth may be spraying, shower diffusion, jet nozzle, etc.
• the gas exhausted from the heating furnace can be reused as high-temperature steam.
• the steam applied to the glass cloth may contain, for example, volatile solvents, water vapor, or gases other than water vapor, but water vapor is preferred from the perspective of reducing toxicity to the human body and facilitating the decomposition of the sizing agent used in the glass fibers.
• the temperature of the high-temperature steam may be such that the surface temperature of the glass cloth is higher than 650°C. In this case, if necessary, a method may be used that allows the high-temperature steam and heated air to be supplied in any ratio.
• the temperature of the high-temperature steam may be 400°C or higher, 450°C or higher, 550°C or higher, 600°C or higher, or 650°C or higher.
• 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 filaments are surface treated using a surface treatment agent having a molecular weight of 200 or more, particularly using a silane coupling agent represented by the above formula (1).
• the silane coupling agent used in the method of this embodiment has a larger molecular weight than general silane coupling agents, and therefore is relatively hydrophobic.
• the present inventors have revealed that when the solvent in the surface treatment liquid contains water, aggregates of the surface treatment agent tend to be easily generated, and that when the solvent in the surface treatment liquid contains water, the frequency of occurrence of white spots on the glass cloth after surface treatment tends to increase.
• the present inventors have found that in a surface treatment solution using a surface treatment agent having a molecular weight of 200 or more, particularly a silane coupling agent represented by the above formula (1), it is possible to form white spots on a glass cloth by taking the following measures (A) to (C): (A) gradually 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 pre-solution of the surface treatment agent can be obtained by adding a small amount of surfactant and solvent (e.g., a 60% aqueous acetic acid solution) to a diluted solution obtained by diluting the surface treatment agent with a small amount of methanol.
• 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 according to the amount of hydrolysis.
• 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 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 process.
• 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 while the surface treatment process is being carried out. 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 glass fiber bundles In the opening process, it is preferable to open the glass fiber bundles using multiple opening methods. This makes it easier to control the average opening degree of the glass cloth within a specified range, even if the glass cloth tends to have poor matrix resin impregnation properties.
• 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, with methanol or toluene being 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.
• Other steps include, for example, a step of processing the glass cloth into slits (slit processing step).
• Test method Another aspect of this embodiment is a test method for a glass cloth made by weaving glass yarns.
• the glass cloth to be tested is surface-treated with a surface treatment agent,
• the above test method is The method includes a step of inspecting the glass cloth for white spots based on the peak height derived from the carbonyl group in the glass cloth and the total carbon content of the glass cloth or the ignition loss value of the glass cloth.
• the glass cloth to be tested the peak height derived from carbonyl groups, the total carbon content, the ignition loss value, and the white spots may be determined by referring to the descriptions in the [Glass Cloth] section above.
• the test method of this embodiment makes it possible to evaluate the properties of the glass cloth based on the white spots that the inventors focused on.
• 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.
• acryloyl groups and methacryloyl groups have good reactivity, it is preferable to use at least one of polyphenylene ether and modified polyphenylene ether as the matrix resin.
• 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 300 ⁇ m thick glass plate was prepared, having the same type and composition as each glass cloth for which the dielectric loss tangent was measured. Then, using the thickness obtained from the glass plate thickness measurement, the bulk dielectric loss tangent at 10 GHz was measured using the same method as for measuring the dielectric loss tangent above.
• 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 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 and the filament diameter of the warp yarn (or the weft yarn) were 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 values of the five measurements obtained were used as the number of filaments and filament diameter of 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).
• Total carbon content (mass%) [ ⁇ mass W (mg) of acetanilide ⁇ (carbon ratio of acetanilide/100) ⁇ / peak area derived from carbon dioxide generated from acetanilide] ⁇ [ ⁇ peak area of carbon dioxide generated from the glass cloth / mass (mg) of the glass cloth ⁇ ⁇ 100] It was calculated based on the following.
• the glass cloth was cut from different positions, and the total carbon content was measured for each of the resulting 10 different samples, and the average value was used as the total carbon content.
• Measurement device Fourier transform infrared spectrophotometer (FT-IR)
• Model Agilent Technologies Variant 670-IR Measurement method: Transmission method Number of integrations: 64 Wavenumber resolution: 4cm -1 Measurement wave number: 400cm -1 ⁇ 4000cm -1
• the baseline was obtained in accordance with the baseline drawing method described in JIS K 0117:2017. Specifically, as shown in Figure 18 d) described in JIS K 0117:2017, a tangent line was drawn to two base points (in this example, the base portion located to the right and left of the peak derived from the carbonyl group in (5) above), and this was treated as the baseline. The difference between the baseline and the peak top was then obtained as the height of the peak derived from the carbonyl group.
• Figure 1 shows the calibration curve L prepared in this example. Of these, Figure 1(a) shows the relationship between peak height and total carbon content, and Figure 1(b) shows the relationship between peak height and loss on ignition value.
• the y-axis value (peak height derived from carbonyl groups) when the total carbon content or ignition loss value of the sample was 0.1 mass% was defined as 1.00.
• the relative values were calculated according to the following formula:
• the "peak height per glass cloth” after the relative value calculation was determined.
• the "peak height per glass cloth” before conversion into a relative value is the "peak height per glass cloth” obtained in (5) above.
• steps (1) to (11) were performed, but as long as the measurement results are not affected, any steps that can be omitted may be omitted, and the order of steps may be reversed.
• the glass cloth was immersed in a surface treatment solution containing a mixture of pure water adjusted to pH 3 with acetic acid and a silane coupling agent (5-hexenyltrimethoxysilane; Z6161 (manufactured by Dow-Toray Industries, Inc.) and 3-methacryloxypropyltrimethoxysilane; Z6030 (manufactured by Dow-Toray Industries, Inc.)).
• a silane coupling agent 5-hexenyltrimethoxysilane; Z6161 (manufactured by Dow-Toray Industries, Inc.) and 3-methacryloxypropyltrimethoxysilane; Z6030 (manufactured by Dow-Toray Industries, Inc.)
• the total mass percentage of the silane coupling agent in the surface treatment solution was adjusted while the mass ratio of 5-hexenyltrimethoxysilane:3-methacryloxypropyltrimethoxysilane was fixed at 1.00:2.83 so that the total carbon content of the sample samples was 0.05 mass%, 0.07 mass%, 0.1 mass%, 0.12 mass%, and 0.15 mass%. Glass cloths were then produced with amounts of silane coupling agent attached that were roughly close to the five points on the calibration curve.
• 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.
• the mother liquor was then 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 would be added in 10 minutes. 5)
• 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 preparing a surface treatment liquid by adding a solvent to a surface treatment agent" of the present disclosure is the mother liquid.
• the mother liquid 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. It is defined as follows.
• 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 P was heated at 1000°C for 15 seconds to perform thermal deoiling (thermal deoiling step).
• the silane coupling agent used was 1,1'-[2-[[(2-Methyl-1-oxo-2-propen-1-yl)oxy]methyl]-2-[6-(trimethoxysilyl)hexyl]-1,3-propanediyl]bis(2-methyl-2-propenoate) (CAS No. 1248412-07-8, Silane Coupling Agent A), and the surface treatment liquid was prepared using the above method so that the concentration of the silane coupling agent in the surface treatment liquid was 0.5% by mass.
• 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 0.22 MPa. The glass cloth was then heated and dried at 135°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 5.0 kg/ cm2 using a spray nozzle, resulting in high-pressure opening.
• ultrasonic waves at a frequency of 25 kHz and an output of 0.60 W/ cm2 were applied in water to further open 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.
• the glass cloth was then immersed in toluene for finish washing, thereby reducing modified silane coupling agent that had not formed chemical bonds with the surface of the glass filaments.
• 2000 m of surface-treated glass cloth was obtained.
• Example 2 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 1, except that acrylic acid, [[2-[(trimethoxysilyl)methoxy]ethyl]imino]diethylene ester (CAS NO: 3390-52-1, silane coupling agent B) was used as the silane coupling agent and the concentration of silane coupling agent B was 0.8 mass%.
• Example 3 As the silane coupling agent, 2-propenoic acid, 1,1'-[2-(8,8-dimethoxy-3-oxo-2,9-dioxa-6-thia-8-siladec-1-yl)-2-[[(1-oxo-2-propen-1-yl)oxy]methyl]-1,3-propanediyl] ester (CAS NO: 1801441-80-4, silane coupling agent C) was used. Except for this, a surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 2.
• Example 4 As the silane coupling agent, 1,1'-[2-Methyl-2-[[[[3-(trimethoxysilyl)propyl]amino]carbonyl]amino]-1,3-propanediyl]di-2-propenoate (CAS NO: 1239892-42-2, silane coupling agent D) was used. Except for this, a surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 2.
• Example 5 A surface-treated glass cloth (2000 m) was obtained in the same manner as in Example 2, except that 2-propenoic acid, 2-methyl-, 1-[(trimethoxysilyl)methyl]-1,2-ethanediyl ester (CAS NO: 143414-45-3, silane coupling agent E) was used as the silane coupling agent.
• Example 6 As a silane coupling agent, 1,1'-[2-[[2-(9,9-Dimethoxy-4-oxo-3,10-dioxa-5-aza-9-silaundec-1-yl)-11,11-dimethoxy-1,6-dioxo-5,12-dioxa-2,7-diaza-11-silatridec-1-yl]amino]-2-methyl-1,3-propanediyl] di-2-propenoate (CAS NO: 1558048-41-1, silane coupling agent F) was used, except that in the same manner as in Example 2, a surface-treated glass cloth of 2000 m was obtained.
• Example 7 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 1, except that glass cloth Q was used and the silane coupling agents A and B were used in a concentration of 0.4% by mass each, totaling 0.8% by mass.
• Example 8 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 1, except that Glass Cloth R was used and the concentration of Silane Coupling Agent A was set to 0.8 mass %.
• Example 9 After the surface treatment, 2000 m of surface-treated glass cloth was obtained in the same manner as in Example 1, except that high-pressure spreading using a spray nozzle was not carried out.
• Example 10 After the surface treatment, 2000 m of surface-treated glass cloth was obtained in the same manner as in Example 1, except that the glass cloth was spread at a high pressure of 2.5 kg/cm 2 using a spray nozzle.
• Example 11 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 1, except that a silane coupling agent of 0.8 mass% in total, consisting of silane coupling agent A and 3-(methacryloyloxy)propyltrimethoxysilane (CAS NO: 2530-85-0, silane coupling agent G) with a concentration of 0.4 mass% each, was used.
• a silane coupling agent of 0.8 mass% in total consisting of silane coupling agent A and 3-(methacryloyloxy)propyltrimethoxysilane (CAS NO: 2530-85-0, silane coupling agent G) with a concentration of 0.4 mass% each, was used.
• Example 1 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 2, except that silane coupling agent G was used.
• Example 2 A surface-treated glass cloth of 2000 m 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.
• Example 3 A surface-treated glass cloth of 2000 m was obtained in the same manner as in Example 2, except that 3-acryloxypropyltrimethoxysilane (CAS No. 4369-14-6, silane coupling agent H) was used as the silane coupling agent.
• silane coupling agent H 3-acryloxypropyltrimethoxysilane
• FIG. 2A and 2B are photographs for explaining the "white spots" in this example.
• Fig. 2A shows a photograph of a portion without a white spot
• Fig. 2B 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 45 parts by mass of polyphenylene ether (Noryl SA9000, manufactured by SABIC Corporation), 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 the Examples and Comparative Examples were impregnated with the prepared varnish and then dried at 115° C. for 1 minute 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 200°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 "failed" laminate samples was evaluated. The fewer the number of glass cloths listed in the table, the more excellent the heat resistance.
• the laminate was cut into a size of 7 cm x 4 cm, and two slits each having a length of 2 cm were made vertically and horizontally using a diamond cutter to prepare test pieces.
• the test pieces were prepared in accordance with the method described in JP 2020-158364 A.
• the resulting test piece was immersed in a 1 mol/L NaOH aqueous solution and heated at 60°C for 30 hours.
• a whitening distance test was then conducted using a digital microscope (Keyence Corporation) at 100x magnification to measure the whitening distance caused by peeling between the resin and glass interface in the warp and weft directions.
• the whitening distance was measured at 24 points in each of the warp and weft directions, and the average value was calculated.
• the whitening distance for each level was evaluated as a relative value, with the value for Comparative Example 1 being set at 1.0. Reducing the whitening distance means improving the insulation reliability of the printed wiring board. The results are shown in the table below.
• the examples provided glass cloth that was capable of achieving excellent dielectric properties and excellent insulation reliability, and also capable of further improving the properties of resin substrates produced using the glass cloth (for example, reducing the whitening distance of the resin substrate).
• none of the comparative examples were able to reduce the whitening distance of the resulting resin substrate, and comparative example 2 in particular 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• Inorganic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Reinforced Plastic Materials (AREA)
• Woven Fabrics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=96544629

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (3)

Family Cites Families (7)

• 2024
  • 2024-10-23 JP JP2025500279A patent/JP7812973B2/ja active Active
  • 2024-10-23 CN CN202480005046.4A patent/CN120693434A/zh active Pending
  • 2024-10-23 WO PCT/JP2024/037673 patent/WO2025158734A1/ja active Pending
  • 2024-10-23 KR KR1020257002793A patent/KR20250117359A/ko active Pending
  • 2024-10-28 TW TW113141093A patent/TW202530155A/zh unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events