Glass filler, method for manufacturing the same, and resin-containing composition comprising the glass filler

Abstract

This invention provides a glass filler, a method for manufacturing the same, and a resin-containing composition comprising the glass filler. The provided glass filler comprises a glass composition containing, by weight percent: 95 ≤ SiO2 ≤ 99.5, 0 ≤ B2O3 ≤ 2, 0.01 ≤ Al2O3 ≤ 4, 0 ≤ R2O ≤ 4, 0.01 ≤ RO ≤ 4, and 0 ≤ TiO2 ≤ 4. Wherein, RO is at least one selected from MgO, CaO, SrO, and ZnO, and R2O is at least one selected from Li2O, Na2O, and K2O. This glass filler can have a dielectric constant of less than 4 at 1 GHz.

Description

[0001] This application is a divisional application of PCT / JP2020 / 034344, application number 202080062280.2, application date: September 10, 2020, entitled "Glass filler and method for manufacturing the same and resin-containing composition comprising glass filler". Technical Field

[0002] This invention relates to glass fillers. Furthermore, this invention relates to methods for manufacturing glass fillers and resin-containing compositions comprising glass fillers. Background Technology

[0003] Glass epoxy boards, a type of printed circuit board, are manufactured by impregnating a resin composition into a glass cloth made of long glass fibers. To meet the miniaturization requirements of electronic devices and the need for thinner profiles with high functionality, the glass cloth requires a low dielectric constant.

[0004] Patent Document 1 discloses a method for increasing the SiO2 content of a glass cloth made of E-glass long fibers by leaching, thereby reducing the dielectric constant of the glass cloth. Leaching is carried out using an acidic solution. After leaching, the glass cloth is washed with water and then heat-treated at 700–800°C. According to an embodiment of Patent Document 1, the dielectric constant of the glass cloth at a frequency of 1 MHz is reduced to approximately 4.4–4.5 by leaching.

[0005] The low dielectric constant of glass cloth can also be achieved by modifying the glass composition. For example, E-glass has a dielectric constant of around 6.6 at 1 MHz, while a modified glass composition called D-glass has a dielectric constant of around 4.0–4.1 at 1 MHz. The dielectric constant of D-glass is also around 4.1–4.2 at 10 GHz, which is low enough even in the high-frequency region.

[0006] The reduction of dielectric constant based on leaching requires treatment with acidic solutions, followed by washing and heating processes, making the process complex and increasing manufacturing costs. For this reason, reducing the dielectric constant of glass cloth through adjustments to the glass composition is relatively advantageous. Based on this, in addition to D-glass, glass compositions with low dielectric constants for long glass fibers have been proposed.

[0007] It should be noted that leaching can also be used to improve the heat resistance of long glass fibers. Patent Document 2 discloses a surface layer with increased SiO2 content formed by leaching E-glass long fibers. In the embodiments of Patent Document 2, the SiO2 content of the surface layer of the E-glass long fibers with a fiber diameter of 9 μm is increased to 90.0 to 93.9% by weight. However, in various embodiments, the SiO2 content of the fiber as a whole, including the interior, is 55.1 to 65.8% by weight. The leaching of Patent Document 2 is implemented such that the SiO2 content in the fiber as a whole, including the interior, does not exceed 80% by weight (claim 2). According to Patent Document 2, the reason for limiting the SiO2 content is that if the glass long fibers as a whole become silica, the strength decreases and they become brittle, or the chemical durability decreases.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2003-34728

[0011] Patent Document 2: Japanese Patent Application Publication No. 7-172876 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] Resin-containing compositions for printed circuit boards include resin and inorganic fillers, and may also include curing agents, modifiers, etc., if desired. Ceramic fillers, glass fillers, etc., can be used as inorganic fillers. However, until now, glass fillers, unlike glass cloth and the long glass fibers used to constitute the glass cloth, have not been sufficiently studied for achieving low dielectric constants. In view of the above, the object of the present invention is to provide a novel glass filler with a low dielectric constant.

[0014] means for solving problems

[0015] This invention provides a glass filler comprising a glass composition.

[0016] The above glass composition comprises, by weight percent:

[0017] 95 ≤ SiO2 ≤ 99.5

[0018] 0≤B2O3≤2

[0019] 0.01≤Al2O3≤4

[0020] 0≤R2O≤4

[0021] 0.01≤RO≤4

[0022] 0≤TiO2≤4,

[0023] Wherein, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

[0024] In other respects, the present invention provides a resin-containing composition comprising: the glass filler of the present invention and the resin.

[0025] The present invention provides, from another aspect, a method for manufacturing the glass filler described above, the method comprising:

[0026] The process of manufacturing a glass filler precursor comprising a master glass composition;

[0027] A process of dissolving at least a portion of the mother glass composition from the glass filler precursor in a manner that yields a glass filler comprising a glass composition different from the aforementioned mother glass composition.

[0028] Invention Effects

[0029] According to the present invention, novel glass fillers with low dielectric constants can be provided. The glass fillers of the present invention are suitable for suppressing the dielectric constant of resin-containing compositions to a low level and for improving various properties of the resin-containing compositions by combining them with glass fillers. These improvements include, for example, increased strength, heat resistance, and dimensional stability; reduced coefficient of linear thermal expansion and anisotropy; and reduced anisotropy of shrinkage during molding. Furthermore, the method according to the present invention enables the efficient manufacture of novel glass fillers with low dielectric constants. Attached Figure Description

[0030] Figure 1A This is a perspective view showing an example of a sheet of glass.

[0031] Figure 1B yes Figure 1A The top view of the sheet of glass shown.

[0032] Figure 2 This is a cross-sectional view showing an example of an apparatus for manufacturing sheet glass.

[0033] Figure 3 This is a cross-sectional view showing a portion of an example of an apparatus for manufacturing chopped raw fibers.

[0034] Figure 4 This is a cross-sectional view showing a portion of an example of an apparatus for manufacturing chopped raw fibers.

[0035] Figure 5 This is a three-dimensional diagram showing an example of a flat fiber.

[0036] Figure 6 This is a perspective view showing another example of flat fibers. Detailed Implementation

[0037] The percentages (%) of each component are expressed in weight %. "Substantially not containing" means a content of less than 0.1% by weight, preferably less than 0.07% by weight, more preferably less than 0.05% by weight, and particularly preferably less than 0.02% by weight. Other preferred ranges for the content and properties of each component can be understood as arbitrary combinations of the upper and lower limits individually stated below. Furthermore, the dielectric constant strictly refers to the relative dielectric constant, but is conventionally referred to as the dielectric constant in this specification. The dielectric constant and relative dielectric constant are values ​​at room temperature (25°C). The following description is not intended to limit the invention, but is presented to illustrate preferred embodiments.

[0038] According to the inventors' research, it is clear that a glass filler with a sufficiently low dielectric constant can be provided. The dielectric constant of this glass filler is lower than that of D-glass. A glass filler with a sufficiently low dielectric constant can be manufactured, for example, by leaching. Unlike long glass fibers, which are structural materials for glass cloth and prioritize strength, glass fillers do not lose their practicality even with sufficient leaching. If leaching is applied, for example, R2O and RO are preferentially removed, significantly reducing the content of these components, and the composition can be changed in such a way that the reduction in the content of TiO2 and Al2O3 is smaller than that of R2O and RO. Such a change in composition is desirable for reducing the dielectric constant. To sufficiently reduce the dielectric constant, it is preferable to reduce the content of R2O to a level that is substantially absent.

[0039] [Composition of the glass composition]

[0040] (SiO2)

[0041] SiO2 is a component that forms the mesh structure of glass. SiO2 has the effect of reducing the dielectric constant of the glass composition. The SiO2 content is preferably 95% or more, 96% or more, 97% or more, more preferably 97.5% or more, and particularly preferably 98% or more. On the other hand, for efficient manufacturing of glass fillers, it is preferable that the glass composition includes components other than SiO2. The SiO2 content can be 99.5% or less, more preferably 99% or less, and depending on the situation, 98.7% or less, particularly 98.5% or less.

[0042] (B2O3)

[0043] B2O3 is also a component that forms the mesh structure of glass. Furthermore, B2O3 is a component that lowers the dielectric constant of the glass composition. However, compositions containing excessive amounts of B2O3 tend to have poor acid resistance. Therefore, the content of B2O3 can be 0.01% or more, 0.05%, or more specifically 0.1% or more. The content of B2O3 can be 2% or less, 1% or less, or more specifically 0.5% or less, and particularly 0.3% or less. B2O3 can be any component, or it can be substantially absent.

[0044] (Al2O3)

[0045] Al₂O₃ is known to improve the chemical durability of glass compositions. The content of Al₂O₃ can be 0.01% or more, 0.05% or more, 0.1% or more, 0.2% or more, and further, 0.3% or more. Although the effect of Al₂O₃ on increasing the dielectric constant is small, if the content is too high, it becomes impossible to obtain a sufficiently low dielectric constant. The content of Al₂O₃ can be 4% or less, 2% or less, 1.5% or less, 1% or less, further, 0.8% or less, particularly 0.6% or less, and depending on the case, 0.5% or less, and further, 0.3% or less.

[0046] (SiO2+B2O3+Al2O3)

[0047] To allow for other components, the combined content of SiO2, B2O3 and Al2O3 can be below 99.8%, below 99.6%, or, depending on the circumstances, below 99.5%.

[0048] (R2O)

[0049] R2O is a component that modifies the mesh structure of the glass. The effect of mesh modification is to reduce the viscosity of the glass composition, and for the glass composition of the filler of the present invention, it makes it easier to obtain a filler with a smoother surface in the heat treatment process after the leaching process. However, compositions containing excessive R2O tend to have poor acid resistance. Therefore, the content of R2O, i.e., the total content of Li2O, Na2O, and K2O, can be 0.01% or more, 0.05% or more, and more preferably 0.1% or more. The content of R2O can be 2% or less, 1% or less, 0.5% or less, and more preferably 0.3% or less. R2O can be any component, or it can be substantially absent. Li2O, Na2O, and K2O can also be substantially absent individually. The content of each of Li2O, Na2O, and K2O can be adjusted individually within the upper and lower limits shown as examples of the content of R2O.

[0050] The following examples illustrate the preferred content of Li2O, Na2O, and K2O (the percentages following the numerical values ​​are omitted; the same applies to this representation below).

[0051] 0≤Li₂O≤1

[0052] 0≤Na2O≤2

[0053] 0≤K2O≤2

[0054] (RO)

[0055] In this embodiment, RO is also a component that improves chemical durability. The content of RO, i.e., the total content of MgO, CaO, SrO, and ZnO, can be 0.01% or more, 0.05% or more, 0.1% or more, 0.2% or more, further 0.3% or more, and particularly 0.4% or more. If the content of RO is too high, it becomes difficult to obtain a sufficiently low dielectric constant. The content of RO can be 4% or less, 2% or less, 1.7% or less, 1.5% or less, further 1% or less, particularly 0.8% or less, and depending on the situation, 0.5% or less. The content of each of MgO, CaO, SrO, and ZnO can be adjusted individually within the upper and lower limits shown as examples of the content of RO.

[0056] RO lowers the devitrification temperature but does not increase the dielectric constant to the same extent as alkali metal oxides R₂O. Therefore, it is preferable to have a higher RO content than R₂O content. However, SrO increases the dielectric constant of the glass composition compared to MgO, CaO, and ZnO. SrO is preferably substantially absent. ZnO may also be substantially absent. MgO has a smaller effect on increasing the dielectric constant compared to CaO. On the other hand, CaO has a greater effect on reducing the viscosity of the glass composition during melting compared to MgO. The ratio of these two components can be appropriately adjusted according to the desired properties. For example, when the dielectric constant is increased by sufficiently increasing the SiO₂ content, the ratio of CaO content to MgO content (CaO / MgO) can be 2 or more, 3 or more, or even 4 or more. However, MgO and CaO, like SrO and ZnO, are arbitrary components. MgO and CaO may also be substantially absent.

[0057] The following examples illustrate the preferred content of MgO, CaO, SrO, and ZnO.

[0058] 0≤MgO≤2

[0059] 0≤CaO≤2

[0060] 0≤SrO≤1

[0061] 0≤ZnO≤2

[0062] The following examples illustrate the preferred content of MgO and CaO.

[0063] 0.05 ≤ MgO ≤ 0.5

[0064] 0.1≤CaO≤1

[0065] (TiO2)

[0066] TiO2 is a component that significantly improves alkali resistance even when added in small amounts. This effect helps improve the durability of the resin against alkali components such as curing catalysts when the filler of the present invention is included in the resin composition. However, compositions containing excessive amounts of TiO2 tend to have an excessively high dielectric constant. If SiO2 is replaced with a trace amount of TiO2, the decrease in dielectric constant can be prevented, and the viscosity of the glass composition can be reduced. The content of TiO2 can be 0.01% or more, 0.05% or more, 0.1% or more, 0.2% or more, further 0.25% or more, and depending on the case, 0.3% or more. The content of TiO2 can be 4% or less, 2% or less, 1.5% or less, 1% or less, further 0.8% or less, particularly 0.6% or less, and depending on the case, 0.5% or less. TiO2 can be any component or can be substantially absent.

[0067] (T-Fe2O3)

[0068] T-Fe2O3 is a component that colors the glass composition. When the glass filler can be colored, it is preferable that the glass composition contains T-Fe2O3; however, when colorlessness is required, the content of T-Fe2O3 can be 0.01% or more, 0.02% or more, or more specifically, 0.05% or more. The content of T-Fe2O3 can be 0.5% or less, 0.3% or less, or more specifically, 0.2% or less. T-Fe2O3 can be any component, or it can be substantially absent. T-Fe2O3 sometimes inevitably mixes into the glass composition from the glass raw material, but by acid treatment as described later, a glass composition substantially free of T-Fe2O3 can be obtained.

[0069] Here, by convention, all iron oxide converted to Fe2O3 is recorded as T-Fe2O3. Therefore, at least a portion of T-Fe2O3 may also be included in the form of FeO.

[0070] (Other ingredients)

[0071] Examples of components other than those mentioned above that can be included in the glass composition include P2O5, BaO, PbO, ZrO2, La2O3, Y2O3, MoO3, WO3, Nb2O5, Cr2O3, SnO2, CeO2, As2O3, Sb2O3, and SO3. Other components that can be included in the glass composition include, for example, noble metal elements such as Pt, Rh, and Os, and halogen elements such as F and Cl. The permissible content of these components is preferably less than 1%, particularly less than 0.5%, and the total is preferably less than 4%, further preferably less than 3%, particularly preferably less than 2%, and especially preferably less than 1%. However, the glass composition may also substantially exclude all of the above-mentioned other components. ZrO2 is sometimes added to glasses with low dielectric constants, but in this embodiment, it may also be substantially excluded. BaO and PbO are preferably substantially excluded. P2O5 is also preferably substantially excluded. This is because BaO and PbO have a significant effect on increasing the dielectric constant of the glass composition, while P2O5 induces phase separation.

[0072] [Preferred Composition Examples of Glass Compositions]

[0073] The following are examples of preferred compositions. The glass composition may substantially contain no components other than those listed below.

[0074] 95≤SiO2≤99

[0075] 0≤B2O3≤2

[0076] 0.01≤Al2O3≤2

[0077] 0≤R2O≤2

[0078] 0.01≤RO≤2

[0079] 0≤TiO2≤2

[0080] [Properties of glass packing]

[0081] (Dielectric constant)

[0082] In a preferred embodiment, the dielectric constant of the glass filler at a frequency of 1 GHz is less than 4, less than 3.97, less than 3.95, less than 3.93, further less than 3.9, and, depending on the case, less than 3.85.

[0083] (Dielectric loss tangent)

[0084] In a preferred embodiment, the dielectric loss tangent of the glass composition of the present invention at a frequency of 1 GHz is 0.0008 or less, 0.0007 or less, and further 0.0006 or less.

[0085] (Surface roughness)

[0086] The surface roughness Ra of the glass filler is, for example, 0 to 100 nm, and particularly preferably 1 to 50 nm. The surface roughness Ra is described in Japanese Industrial Standard (JIS) B0601-2001. According to the inventors' research, the leaching process described later sometimes increases the surface roughness Ra of the glass filler; it is preferable to achieve Ra to the extent described above by a heating process following the leaching process.

[0087] (Specific surface area)

[0088] The specific surface area of ​​the glass filler is preferably, for example, 0.03 to 10 m². 2 / g, preferably 0.05~2m 2 / g, more preferably 0.1–1.5m 2 / g. Specific surface area can be determined, for example, by the BET method (nitrogen adsorption method).

[0089] (Volume of fine pores)

[0090] The pore volume of the glass packing is preferably 0 to 0.1 cm³. 3 / g, preferably 0.0005~0.05cm 3 / g, more preferably 0.001~0.015cm 3 / g. Pore volume can be determined, for example, by the BET method (nitrogen adsorption method). Here, "pore volume" refers to the total pore volume based on the BET method.

[0091] [Glass filler]

[0092] (Morphology of glass packing)

[0093] The morphology of the glass filler is not particularly limited; for example, it can be a form equivalent to at least one selected from sheet glass, chopped filaments, ground fibers, glass powder, glass beads, flat fibers, and thin sheet glass. However, there is no strict distinction between these forms. Furthermore, two or more glass fillers with different morphologies can be combined and used as fillers. It should be noted that the glass filler can have a fibrous shape or other shapes; when it has a fibrous shape, a fiber length of 30 mm or less, 10 mm or less, further 5 mm or less, and particularly less than 3 mm is preferred. However, longer glass fillers are also acceptable. The various forms will be described below.

[0094] Flake glass, also known as sheet glass, has a sheet-like shape. The average thickness of flake glass is, for example, 0.1–15 μm. Figure 1A As shown, the thickness of the sheet glass is equivalent to the distance t between the two principal surfaces of the sheet glass 10. Figure 1BThe diagram shows the main surface of a sheet of glass 10 with an area S. The average particle size is, for example, 0.2–15000 μm. The aspect ratio of the sheet of glass is, for example, 2–1000. The aspect ratio can be obtained by dividing the average particle size by the average thickness. The average thickness can be obtained by measuring the thickness t of more than 100 sheet pieces using a scanning electron microscope (SEM) and calculating their average value. The average particle size of the sheet of glass can be determined based on the particle size (D50) that represents the 50% cumulative volume percentage in the particle size distribution determined by laser diffraction scattering.

[0095] Sheet glass can be obtained using known methods such as glass blowing and cupping. A manufacturing apparatus using the glass blowing method is shown below. Figure 2 In this apparatus, glass preform 11, which is molten in a refractory furnace 12 and has a predetermined composition, expands into a balloon shape due to gas being blown to a nozzle 13, becoming a hollow glass membrane 14. The hollow glass membrane 14 is then crushed by a pair of extrusion rollers 15 to obtain sheet glass 10.

[0096] Chopped strands have a shape in which glass fibers are cut to a relatively short length. The fiber diameter of chopped strands is, for example, 1–50 μm, and its aspect ratio is, for example, 2–1000. The aspect ratio of chopped strands can be determined by dividing the fiber length by the fiber diameter. Chopped strands can, for example, use... Figure 3 and Figure 4 The apparatus shown is used to manufacture it.

[0097] like Figure 3 As shown, a glass preform, molten in a refractory furnace and having a specified composition, is drawn out from a perforator 20 with multiple (e.g., 2400) nozzles at the bottom, as a large number of glass filaments 21. After cooling water is blown onto the glass filaments 21, an adhesive (bundling agent) 24 is applied by a coating roller 23 of an adhesive feeder 22. The large number of glass filaments 21 coated with adhesive 24 are bundled by a reinforcing pad 25 into three filaments 26, each containing, for example, about 800 glass filaments 21. Each filament 26 is wound onto a cylindrical tube 29 that is oscillated by a lateral pavers 27 and embedded in a collet 28. The cylindrical tube 29 with the filaments 26 wound on it is removed from the collet 28, resulting in a filament roll (filament roll) 30.

[0098] Next, as Figure 4 As shown, the yarn cake 30 is placed in the spool holder 31, and the raw yarn 26 is pulled out from the yarn cake 30 and bundled into a raw yarn bundle 33 by the bundling guide 32. Water or treatment liquid is sprayed onto the raw yarn bundle 33 by the spraying device 34. The raw yarn bundle 33 is cut by the rotating blade 36 of the cutting device 35 to obtain chopped raw yarn 37.

[0099] The abrasive fiber has the shape of glass fiber cut into powder. The fiber diameter of the abrasive fiber is, for example, 1–50 μm, and its aspect ratio is, for example, 2–500. The aspect ratio of the abrasive fiber can be obtained by dividing the fiber length by the fiber diameter. The abrasive fiber can be obtained by known methods.

[0100] Glass powder is a powdered form of glass, manufactured by processing glass. The average particle size of glass powder is, for example, 1–500 μm. The particle size of glass powder is defined as the diameter of a sphere with the same volume as the glass powder particles. Glass powder can be obtained by known methods.

[0101] Glass beads have a spherical or nearly spherical shape. The average particle size of glass beads is, for example, 1–500 μm. The particle size of a glass bead is defined as the diameter of a sphere with the same volume as the glass bead particles. Glass beads can be obtained by known methods.

[0102] Flat fibers are formed by cutting glass fibers with a flat cross-section, such as an ellipse. For example... Figure 5 As shown, relative to the minor axis D1 of the flat fiber cross-section, the major axis D2 is larger, and the D2 / D1 ratio is, for example, 1.2 or greater. The minor axis D1 is, for example, 0.5–25 μm. The major axis D2 is, for example, 0.6–300 μm. The length L of the flat fiber is, for example, 10–1000 μm. Flat fibers can be obtained by known methods. Figure 6 As shown, the cross-sectional shape of a flat fiber can have a concave shape where the surface extending along the major axis D2 recedes in the middle compared to the ends.

[0103] Thin sheet glass is a sheet of glass with a thin profile. For example, thin sheet glass can be composed of sheet glass with an average thickness of 0.1 to 2.0 μm. Alternatively, it can contain sheet glass with a thickness in the range of 0.01 to 2.0 μm in a proportion of 90% by mass or more. Thin sheet glass with such a thin average thickness and small thickness deviation is highly effective in reinforcing resin and also excellent in reducing the molding shrinkage rate of the resin.

[0104] Thin sheet glass is also suitable for applications where restrictions on the thickness of resin molded bodies are relaxed compared to previous methods. The thin sheet glass is preferably composed of sheet glass with an average thickness of 0.1 to 1.0 μm. Preferably, the thin sheet glass contains sheet glass with a thickness in the range of 0.05 to 1.0 μm in a proportion of 90% by mass or more. The thin sheet glass can be obtained by the methods described above.

[0105] (Granulation of glass fillers)

[0106] Glass fillers can be at least partially granulated. Granulation is a process of treating glass fillers with an adhesive, binding the individual glass fillers together and granulating them. Granular glass fillers have excellent workability and dispersion in resins due to their low dispersion. Using granular glass fillers improves feedability and enables more reliable metering. The adhesive used for granulation is described below.

[0107] The adhesive preferably contains a surfactant and a binding component. The surfactant can be any of anionic, cationic, amphoteric, or nonionic surfactants. When the binding component contains an epoxy resin or polyurethane resin, a nonionic surfactant is preferred. This is because it can inhibit the aggregation of the adhesive and stabilize it. Examples of anionic surfactants include sodium dioctyl sulfosuccinate, fatty acid salts, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl allyl sulfates, and sulfosuccinates. Examples of cationic surfactants include higher amine halides, haloalkylpyridinium, or quaternary ammonium salts. Examples of amphoteric surfactants include lauryl aminopropionate and lauryl dimethyl betaine. Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether and other polyoxyethylene glycol alkyl ethers, polyethylene glycol monostearate and other polyethylene glycol fatty acid esters, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate and other sorbitan fatty acid esters, glycol monostearate and other glycol fatty acid esters, and fatty acid monoglycerides. Two or more of these surfactants can also be used in combination.

[0108] The binding components of the adhesive are not particularly limited and can be either organic or inorganic. Examples of organic binding components include methylcellulose, carboxymethylcellulose, starch, carboxymethyl starch, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, silane coupling agents, acrylic resins, epoxy resins, phenolic resins, vinyl acetate, and polyurethane resins. Examples of inorganic binding components include water glass, colloidal silica, colloidal alumina, and aminosilanes. Preferably, the binding component includes at least one selected from silane coupling agents, epoxy resins, and polyurethane resins. Silane coupling agents have two or more reactive groups in their molecules, one of which reacts with the surface of the sheet glass, and the other reacts with the organic binding components and the thermoplastic resin; therefore, the fusion of the sheet glass and the thermoplastic resin is improved. Epoxy resins and polyurethane resins fuse well with silane coupling agents and thermoplastic resins.

[0109] For the adhesive, water or alcohol is preferably used as the solvent, and its concentration is adjusted in such a way that each component can exist uniformly on the surface of the glass filler. The concentration of the adhesive, expressed as the total solids concentration, is preferably 1 to 10% by mass. The adhesive can be manufactured, for example, by appropriately adding the binding components, surfactants, etc., to the solvent at room temperature and atmospheric pressure and stirring until homogeneous.

[0110] The proportion of binder in the granulated glass filler, in other words, the adhesion rate of the binder, is, for example, 0.1 to 2% by mass of the solid components. An adhesion rate of 0.1% by mass or more is suitable for sufficiently suppressing the dispersion of the glass filler. An adhesion rate of less than 2% by mass is suitable for suppressing gas generation and discoloration of the resin-containing composition during extrusion molding.

[0111] There are no particular limitations on the method for granulating glass fillers. For example, stirring granulation, fluidized bed granulation, spray granulation, and rotary granulation can be used. Specifically, the following method can be applied: a suitable amount of glass filler with a binder is spread in a rotating drum or vibrating tray by spraying, and the solvent is evaporated by heating, while granulation occurs simultaneously. By appropriately adjusting the rotation speed of the drum or the vibration frequency of the vibrating tray, and thus appropriately adjusting the solvent evaporation rate, glass filler particles of the desired size can be manufactured.

[0112] Glass fillers can be products whose surfaces have been treated with a surface treatment agent. Sometimes, this treatment improves the reinforcing effect of the glass filler. Examples of surface treatment agents include, for instance, silicon-based coupling agents such as γ-aminopropyltriethoxysilane, vinyltriethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane, as well as titanium-based coupling agents. The amount of surface treatment agent used is, for example, 0.05 to 0.20% by mass of the glass filler.

[0113] [Manufacturing method of glass filler]

[0114] The glass filler manufacturing method of this embodiment includes: a step of manufacturing a glass filler precursor, and a step of dissolving at least a portion of the parent glass composition from the glass filler precursor.

[0115] (Manufacturing process of glass filler precursor)

[0116] In this process, a glass filler precursor is manufactured. The glass filler precursor can be manufactured using known methods appropriate to the type of glass filler. The glass filler precursor is typically manufactured by melting and shaping a glass raw material into a predetermined shape. There are no particular limitations on the composition of the parent glass contained in the glass filler precursor, as long as the final glass composition desired can be obtained. An example of a preferred parent glass composition is described below.

[0117] Preferred mother glass compositions include, for example, the following components.

[0118] 52≤SiO2≤57

[0119] 5≤B2O3≤12

[0120] 12≤Al2O3≤17

[0121] 0≤R2O≤3

[0122] 15≤RO≤30

[0123] 0≤TiO2≤3

[0124] 0≤T-Fe2O3≤1

[0125] (The dissolution process consisting of mother glass)

[0126] In this process, at least a portion of the master glass composition is dissolved from the glass filler precursor to produce the glass filler. Through dissolution, the glass filler comprises a glass composition with a different composition from the master glass composition. In this dissolution process, the SiO2 content contained in the glass filler becomes relatively higher. In other words, the SiO2 content of the glass composition contained in the glass filler is higher by weight than the SiO2 content of the master glass composition by weight.

[0127] The dissolution process can be carried out, for example, by contacting the glass filler precursor with an acidic solution. The acidic solution can be an organic acid in addition to inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid. Preferred acidic solutions are inorganic acids, specifically hydrochloric acid and / or nitric acid, particularly hydrochloric acid. Hydrochloric acid can be used, for example, at a concentration of 1 to 6 equivalents (1 to 6N).

[0128] The method of contacting the glass packing precursor with the acidic solution is not particularly limited; for example, it can be carried out by immersing the glass packing precursor in an acidic solution held in a container. It is preferable to heat the acidic solution to be in contact with the glass packing precursor. A preferred temperature of the acidic solution is 40–90°C, particularly 70–90°C. The contact time between the glass packing precursor and the acidic solution is not particularly limited, but depends on the concentration and temperature of the acidic solution, for example, 1–48 hours.

[0129] Although it also depends on the composition of the mother glass, in the leaching process, 30-60%, especially 40-50%, of the glass filler precursor can be dissolved by weight. In order to sufficiently reduce the dielectric constant, it is desirable to preferentially and substantially dissolve components other than SiO2, thereby sufficiently increasing the SiO2 content.

[0130] After the leaching process, a drying process is performed as needed to remove moisture and acid components from the glass filler. The drying process can be performed by heating the glass filler to a temperature range of 50–200°C, preferably 80–180°C. More preferably, a firing process is performed after the leaching process, followed by any drying process. The firing process is not particularly limited, but a heating process at 100°C or higher, more preferably 1000–1300°C for 15 minutes to 12 hours, and even more preferably 1150–1200°C for 30 minutes to 4 hours is preferred. If the heating temperature is too low or too short, the surface roughness of the glass filler becomes coarse, for example, the specific surface area exceeds 2.0 μm². 2 / g, or a pore volume exceeding 5.0 × 10⁻⁶. -2 cm 3 / g. On the other hand, if the temperature of the heating process is too high, the glass filler may deform or, in severe cases, fuse together.

[0131] [Glass cloth]

[0132] The glass composition described above, present in this embodiment of the glass filler, is also suitable for use as a glass cloth. Furthermore, the aforementioned properties of the glass filler of this embodiment are also desirable properties for a glass cloth. In other aspects, the present invention provides a glass cloth having the aforementioned glass composition and / or the aforementioned properties, and further provides long glass fibers having the aforementioned glass composition and / or the aforementioned properties. In the aforementioned prior art regarding glass cloth, sufficient research has not been conducted regarding its composition and properties.

[0133] In the glass cloth of the present invention, the glass composition constituting these glass cloths is as described above. In a preferred embodiment, the glass composition may substantially not contain B2O3. The glass composition may substantially not contain R2O. The glass composition may also contain trace amounts (e.g., more than 0.01%) of TiO2. Many properties of the glass cloth of the present invention are as described above. The dielectric constant of the glass cloth of the present invention at a frequency of 1 GHz can be less than 4. Furthermore, the specific surface area can also be adjusted to 2.0 m². 2 / g or less. The pore volume can also be adjusted to 5.0×10 -2 cm 3 / g or less. The same applies to the long glass fibers of this invention.

[0134] The glass cloth and glass fibers of the present invention can be manufactured according to the glass filler manufacturing method described above. For example, for the glass cloth, firstly, glass fibers are manufactured by a leaching process in which at least a portion of the parent glass composition is dissolved from the glass fiber precursor. After the leaching process, a drying process and a heating process are appropriately performed as described above. Then, the obtained glass fibers are used to manufacture the glass cloth according to a known method. The leaching process can also be performed on a glass cloth precursor formed prior to the glass fibers.

[0135] [Glass mat]

[0136] The glass filler of this invention can also be used in the form of a glass mat. Glass cloth is woven fabric, while the glass mat is nonwoven fabric. The glass mat typically contains chopped strands, but may also contain glass fillers of other shapes. The glass mat may contain both glass filler and adhesive. The glass mat may contain resin and other short fibers.

[0137] [Resin-containing composition]

[0138] The resin-containing composition of the present invention comprises the glass filler of the present invention as well as a resin. The resin can be a thermoplastic resin or a thermosetting resin. Thermoplastic resins are not particularly limited, and examples include polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutene, polybutylene terephthalate, copolymers thereof, etc. If polybutylene terephthalate is used, the effect of suppressing warpage and improving dimensional stability of the molded article due to mixing with the glass filler is greater. Thermosetting resins are not particularly limited, and include phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, polyimides, etc.

[0139] The resin-containing composition of the present invention is not particularly limited, and may be, for example, a resin-containing composition referred to as sheet molding plastic, integral molding plastic, etc. The glass filler of the present invention may be included in the resin-containing composition in a dispersed state, or may be included in a molded body such as a glass pad.

[0140] The content of glass fillers such as sheet glass in the resin-containing composition is preferably 5 to 70% by mass. By setting it to 5% by mass or more, it becomes easier to fully exert its function as a reinforcing material for the glass filler. By setting it to 70% by mass or less, it becomes easier to uniformly disperse the glass filler in the resin-containing composition. In order to sufficiently suppress molding shrinkage, the content of glass filler is set to 30% by mass or more.

[0141] Reinforcing materials other than glass fillers can be appropriately contained in resin-containing compositions. For example, in applications requiring high strength, long glass fibers may be included. In this case, the long glass fibers can be added at the same level as the glass fillers.

[0142] Sheet glass, flat fibers, and thin sheet glass have relatively large specific surface areas, which are suitable for ensuring bonding strength with thermoplastic resins. From this perspective, Figure 6 The flat fibers shown are preferred because their concave surface shape helps to increase the specific surface area.

[0143] Other embodiments of the resin-containing composition of the present invention include the glass cloth of the present invention while also containing resin. An example of this embodiment is a prepreg. In this embodiment, the resin described above may also be used.

[0144] The resin-containing composition of the present invention has a low dielectric constant and is suitable for improving numerous properties such as strength, heat resistance, dimensional stability, reduced linear thermal expansion coefficient, reduced anisotropy, and reduced anisotropy of shrinkage during molding. The resin-containing composition of the present invention can be molded into a molded body having a shape suitable for its application. The resin-containing composition of the present invention is used, for example, in communication devices and their peripheral components due to its low dielectric properties.

[0145] Example

[0146] The present invention will now be described in more detail through embodiments. The present invention is not limited to the following embodiments.

[0147] (Example 1)

[0148] First, use Figure 2 The apparatus shown manufactures sheet-like glass bodies, which are then graded to produce glass filler precursors. The glass raw materials are formulated with the following composition: SiO2 53.5%, B2O3 8.5%, Al2O3 15%, Na2O 0.2%, K2O 0.2%, MgO 4.5%, CaO 17.5%, TiO2 0.4%, and T-Fe2O3 0.2%. Next, the glass filler precursor is immersed in 9% hydrochloric acid heated to 82°C for 6 hours, then thoroughly washed with deionized water, and further dried in a hot-air circulating electric drying chamber at 180°C for 6 hours. It is then further heated in an electric furnace set to 1150°C for 8 hours. The sheet glass obtained after acid treatment and heating has the composition shown in Table 1, and its weight is reduced by 45.7% compared to before acid treatment.

[0149] (Example 2)

[0150] The mother glass composition was set as follows: SiO2 53.2%, B2O3 9%, Al2O3 14.6%, Li2O 0.6%, Na2O 0.6%, K2O 0.2%, MgO 0.5%, CaO 21.1%, and T-Fe2O3 0.2%. Except for these other characteristics, sheet glass was obtained in the same manner as in Example 1. The sheet glass had the composition shown in Table 1, and its weight was reduced by 46.3% compared to before acid treatment.

[0151] (Example 3)

[0152] The mother glass composition was set as follows: SiO2 53%, B2O3 8%, Al2O3 14%, MgO 4%, CaO 20%, TiO2 0.6%, and T-Fe2O3 0.4%. Except for these other characteristics, sheet glass was obtained in the same manner as in Example 1. The sheet glass had the composition shown in Table 1, and its weight was reduced by 45.9% compared to before acid treatment.

[0153] (Comparative Example 1)

[0154] The sheet glass prepared in Example 1 before acid treatment was used directly as glass filler.

[0155] (Comparative Example 2)

[0156] Commercially available glass fibers composed of D-glass are used directly as glass fillers.

[0157] (Average thickness and average particle size)

[0158] The sheet glass samples of Examples 1-3 were measured using a laser microscope (Lasertec, product name: OPTELICS HYBRID). Specifically, the grain size of the sheet glass was calculated as the arithmetic mean of the maximum diameter when viewed from above the main surface and the diameter in a direction orthogonal to it within the main surface. The average grain size was calculated as the arithmetic mean of the grain sizes of 50 different sheet glass samples. The average thickness was calculated as the arithmetic mean of the thicknesses of 50 different sheet glass samples viewed from the thickness direction. The same measurements were also performed on the sheet glass samples of Examples 1-3 before acid treatment. The measured values ​​are shown in Table 1.

[0159] (Dielectric constant and dielectric loss tangent)

[0160] The dielectric constant and dielectric loss tangent at various frequencies were measured using a dielectric constant measuring device based on the cavity resonator perturbation method. The measurement temperature was 25°C, and the sample size was set as a cuboid with a square base of 1.5 cm on each side and a length of 10 cm. It should be noted that the sample was made into the aforementioned cuboid shape by compressing the glass filler in a pressing mold using hydraulic pressure. This sample has voids, and its measured value does not directly represent the true value of the glass filler. However, the true value of the glass filler was calculated by converting the void portion into air. The true density of the glass filler was determined using the Archimedes method with kerosene as the impregnating liquid. The apparent density of the sample was obtained by dividing its weight by the volume calculated using a micrometer and vernier caliper. The porosity of the sample was then calculated, and the true value of the glass filler was calculated by treating the volume equivalent to the porosity as air. The measured values ​​of the dielectric constant and dielectric loss tangent are shown in Table 1.

[0161] (Arithmetic mean roughness)

[0162] The arithmetic mean roughness Ra, as specified in JIS B 0601-2001, was evaluated on the main surface of the sheet glass of Example 1, and the result was 0.01 μm. The sheet glass of Example 1 has a surface as smooth as the forged surface of Comparative Example 1 (the glass filler precursor of Example 1, before acid treatment).

[0163] (Specific surface area, etc.)

[0164] For Comparative Example 1 (the glass filler precursor of Example 1, before acid treatment), Reference Example 1 (acid treatment was performed in Example 1 without subsequent heat treatment after drying), and the sheet glass of Example 1, the specific surface area, pore volume, and porosity were determined by the BET method (nitrogen adsorption method). For Reference Example 1, the average pore diameter was calculated. The results are shown in Table 2.

[0165] [Table 1]

[0166]

[0167] [Table 2]

[0168]

Claims

1. A glass filler comprising a glass composition, The glass composition comprises, by weight percent: 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O < 0.05 0.2≤RO≤4 0≤TiO2≤4, in, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

2. A glass filler comprising a glass composition, The glass composition comprises, by weight percent: 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O < 0.05 0.01≤RO≤4 0≤TiO2≤4, in, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

3. A glass filler comprising a glass composition, The glass composition comprises, by weight percent: 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O < 0.05 0.01≤RO≤4 0.1≤TiO2≤4, in, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

4. The glass filler according to any one of claims 1 to 3, wherein, The dielectric constant at a frequency of 1 GHz is less than 4.

5. The glass filler according to any one of claims 1 to 3, wherein, The surface roughness Ra is 0 nm to 100 nm.

6. The glass filler according to any one of claims 1 to 3, wherein, Specific surface area is 0.03 m² 2 / g~10m 2 / g.

7. The glass filler according to any one of claims 1 to 3, wherein, The pore volume is 0 cm³ 3 / g~0.1cm 3 / g.

8. The glass filler according to any one of claims 1 to 3, wherein, It is equivalent to at least one selected from sheet glass, chopped filaments, ground fibers, glass powder and flat fibers.

9. A glass filler comprising a glass composition, The glass filler is sheet glass. The dielectric constant at a frequency of 1 GHz is less than 4. The glass composition comprises, by weight percent: (a), (b), or (c). (a) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.2≤RO≤4 0≤TiO2≤4, (b) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O ≤ 0.5 0.01≤RO≤4 0≤TiO2≤4, (c) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.01≤RO≤4 0.1≤TiO2≤4 Wherein, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

10. A glass filler comprising a glass composition, The glass filler is chopped filament. The dielectric constant at a frequency of 1 GHz is less than 4. The glass composition comprises, by weight percent: (a), (b), or (c). (a) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.2≤RO≤4 0≤TiO2≤4, (b) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O ≤ 0.5 0.01≤RO≤4 0≤TiO2≤4, (c) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.01≤RO≤4 0.1≤TiO2≤4 Wherein, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

11. A glass filler comprising a glass composition, The glass filler is ground fiber. The dielectric constant at a frequency of 1 GHz is less than 4. The glass composition comprises, by weight percent: (a), (b), or (c). (a) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.2≤RO≤4 0≤TiO2≤4, (b) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O ≤ 0.5 0.01≤RO≤4 0≤TiO2≤4, (c) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.01≤RO≤4 0.1≤TiO2≤4, Wherein, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

12. The glass packing according to claim 8, wherein, It is glass powder.

13. A glass filler comprising a glass composition, The glass filler is a flat fiber. The dielectric constant at a frequency of 1 GHz is less than 4. The glass composition comprises, by weight percent: (a), (b), or (c). (a) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.2≤RO≤4 0≤TiO2≤4, (b) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0 ≤ R2O ≤ 0.5 0.01≤RO≤4 0≤TiO2≤4, (c) 95 ≤ SiO2 ≤ 99.5 0≤B2O3≤2 0.01≤Al2O3≤4 0≤R2O≤4 0.01≤RO≤4 0.1≤TiO2≤4 Wherein, RO is selected from at least one of MgO, CaO, SrO and ZnO, and R2O is selected from at least one of Li2O, Na2O and K2O.

14. A resin-containing composition comprising: a glass filler according to any one of claims 1 to 3, and a resin.

15. A method for manufacturing a glass filler, as described in any one of claims 1 to 3, comprising: The process of manufacturing a glass filler precursor comprising a master glass composition; and The process of dissolving at least a portion of the mother glass composition from the glass filler precursor in a manner that yields a glass filler comprising a glass composition different from the mother glass composition. The mother glass composition comprises, by weight percent: 52≤SiO2≤57 5≤B2O3≤12 12≤Al2O3≤17 0≤R2O≤4 15≤RO≤30 0≤TiO2≤4 0≤T-Fe2O3≤1。

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