WO2020241122A1 - 表面改質ガラス、電子部品、及び、ケイ酸塩皮膜の形成方法 - Google Patents

表面改質ガラス、電子部品、及び、ケイ酸塩皮膜の形成方法 Download PDF

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Publication number
WO2020241122A1
WO2020241122A1 PCT/JP2020/017226 JP2020017226W WO2020241122A1 WO 2020241122 A1 WO2020241122 A1 WO 2020241122A1 JP 2020017226 W JP2020017226 W JP 2020017226W WO 2020241122 A1 WO2020241122 A1 WO 2020241122A1
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WIPO (PCT)
Prior art keywords
glass
silicate film
silicate
coating agent
present
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Ceased
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PCT/JP2020/017226
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English (en)
French (fr)
Japanese (ja)
Inventor
紀行 大川
善行 野村
智彦 森
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to KR1020217031442A priority Critical patent/KR102625407B1/ko
Priority to CN202080037089.2A priority patent/CN113840812B/zh
Priority to JP2021522707A priority patent/JP7156520B2/ja
Publication of WO2020241122A1 publication Critical patent/WO2020241122A1/ja
Priority to US17/496,373 priority patent/US12497326B2/en
Anticipated expiration legal-status Critical
Priority to US19/388,017 priority patent/US20260070840A1/en
Ceased legal-status Critical Current

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    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/18—Compositions for glass with special properties for ion-sensitive glass
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/02—Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H01C1/034—Housing; Enclosing; Embedding; Filling the housing or enclosure the housing or enclosure being formed as coating or mould without outer sheath
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/28—Coils; Windings; Conductive connections
    • H01F27/32—Insulating of coils, windings, or parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/228—Other specific oxides
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion

Definitions

  • the present invention relates to surface-modified glass, electronic components, and a method for forming a silicate film.
  • Patent Document 1 describes that in water-repellent glass having a silicone-based resin film on the surface of a glass substrate, the silicone-based resin is hydrolyzed by an alkaline component eluted from the glass substrate, and the water repellency is lowered. ing.
  • the elution of glass components as described above also poses a problem in electronic components such as multilayer ceramic capacitors.
  • Glass may be present on the surface of the ceramic element or the external electrode that constitutes an electronic component such as a multilayer ceramic capacitor.
  • the glass component may be eluted from the portion where the glass is present on the surface. If water penetrates into the portion where the glass component is eluted, the electrical insulation and life characteristics are deteriorated, and as a result, the moisture resistance reliability of the electronic component is lowered.
  • the above problem is not limited to electronic components, but is a problem common to articles in which the glass component may elute from the glass existing on the surface.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a surface-modified glass in which a silicate film capable of suppressing elution of glass components is provided on the surface of the glass. And. It is also an object of the present invention to provide an electronic component in which the silicate film is provided on the surface of glass, and to provide a method for forming the silicate film on the surface of glass.
  • the surface-modified glass of the present invention is a surface-modified glass comprising a glass and a silicate film provided on the surface of the glass, and the glass contains at least one polyvalent metal ion.
  • the silicate film contains polyvalent metal ions common to the glass.
  • the electronic component of the present invention is an electronic component including a ceramic element and an electrode layer provided on a part of the surface of the ceramic element, and is formed on at least one surface of the ceramic element and the electrode layer.
  • Glass exists, and a silicate film is provided on the surface of the glass.
  • the glass contains at least one polyvalent metal ion, and the silicate film is a polyvalent metal common to the glass. Contains ions.
  • the method for forming a silicate film of the present invention comprises a step of applying a coating agent containing an alkali metal silicate to the surface of a glass containing at least one type of polyvalent metal ion, and the above-mentioned multiple contained in the glass. By eluting the valent metal ions on the surface of the glass, a silicate film containing the polyvalent metal ions common to the glass is formed on the surface of the glass.
  • the multivalent metal ion means a metal ion having a valence of 2 or more.
  • a silicate film capable of suppressing elution of glass components can be formed on the surface of glass.
  • FIG. 1 is a side view schematically showing an example of the surface-modified glass of the present invention.
  • FIG. 2 is a side view schematically showing an example of a multilayer ceramic capacitor in which glass is present on the surface of an external electrode.
  • FIG. 3 is a side view schematically showing an example of a multilayer ceramic capacitor in which glass is present at the interface between the external electrode and the ceramic element.
  • FIG. 4 is a side view schematically showing an example of a multilayer ceramic capacitor in which glass is present on the surface of the ceramic body.
  • FIG. 5 is a side view schematically showing another example of a multilayer ceramic capacitor in which glass is present on the surface of the ceramic body.
  • FIG. 6 is an enlarged side view schematically showing an example of a multilayer ceramic capacitor in which glass is present on the surface of a ceramic body or an external electrode.
  • FIG. 7 is a TEM image showing a part of the external electrode formed on the sample of Example 2.
  • FIG. 8 is an enlarged TEM image of the portion surrounded by the broken line in FIG. 7.
  • FIG. 9 is a graph showing the composition of the film and glass constituting the sample of Example 2.
  • the present invention is not limited to the following configurations, and can be appropriately modified and applied without changing the gist of the present invention. It should be noted that a combination of two or more of the individual desirable configurations described below is also the present invention.
  • FIG. 1 is a side view schematically showing an example of the surface-modified glass of the present invention.
  • the surface-modified glass 1 shown in FIG. 1 includes a glass 2 and a silicate film 3.
  • the silicate film 3 is provided on the surface of the glass 2.
  • the glass constituting the surface-modified glass of the present invention contains at least one type of multivalent metal ion.
  • the polyvalent metal ion for example, at least one ion selected from the group consisting of Be, Mg, Ca, Sr, Ba, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga and Sn. And so on.
  • ions such as polyvalent metal ions contained in the glass are analyzed by analyzing the composition of the surface-modified glass by a transmission electron microscope-energy dispersive X-ray spectroscopy (TEM-EDX). , Can be confirmed by analyzing the types of elements contained in the glass.
  • TEM-EDX transmission electron microscope-energy dispersive X-ray spectroscopy
  • the valence of the multivalent metal ion contained in the glass may fluctuate, but it is sufficient to analyze the type of the element contained in the glass, and it is not necessary to analyze the valence.
  • the same method can be used for the electronic component of the present invention and the method for forming a silicate film.
  • the glass constituting the surface-modified glass of the present invention may further contain at least one monovalent metal ion.
  • the monovalent metal ion include at least one ion selected from the group consisting of Li, Na, K, Rb and Cs.
  • the type of glass constituting the surface-modified glass of the present invention is not particularly limited, and examples thereof include borosilicate glass.
  • the shape of the glass is not particularly limited. Further, the surface-modified glass of the present invention also includes an article in which glass is present on a part of the surface and a silicate film is provided on the surface of the glass.
  • the silicate film constituting the surface-modified glass of the present invention contains polyvalent metal ions common to glass.
  • the silicate film constituting the surface-modified glass of the present invention is preferably formed by the [method for forming a silicate film] described later.
  • the silicate film since the silicate film is formed by the reaction of the polyvalent metal ion contained in the glass with the silicate ion, the silicate film contains the polyvalent metal ion derived from the glass.
  • examples of the polyvalent metal ions commonly contained in the glass and the silicate film include Be, Mg, Ca, Sr, Ba, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ga. And at least one ion selected from the group consisting of Sn and the like.
  • ions such as polyvalent metal ions contained in the silicate film are the types of elements contained in the silicate film by analyzing the composition of the surface-modified glass by TEM-EDX. Can be confirmed by analyzing.
  • the valence of the multivalent metal ion contained in the silicate film may fluctuate, but it is sufficient to analyze the type of element contained in the silicate film, and it is not necessary to analyze the valence.
  • the same method can be used for the electronic component of the present invention and the method for forming a silicate film.
  • the content of the multivalent metal ion contained in the silicate film is not particularly limited.
  • the interface between the silicate film and the glass can be confirmed by cross-sectional observation using TEM. Therefore, when the composition of the surface-modified glass is analyzed in the depth direction from the surface of the silicate film toward the inside of the glass by the method described above, the content of each ion at the interface between the silicate film and the glass. It is sufficient to confirm whether the number increases or decreases.
  • the silicate film constituting the surface-modified glass of the present invention may further contain at least one monovalent metal ion.
  • the monovalent metal ion contained in the silicate film may or may not be common with glass.
  • the silicate film constituting the surface-modified glass of the present invention may contain other glass components.
  • the silicate film may contain B (boron) ions.
  • the electronic component of the present invention includes a ceramic body and an electrode layer provided on a part of the surface of the ceramic body.
  • glass is present on at least one surface of the ceramic body and the electrode layer, and a silicate film is provided on the surface of the glass.
  • the electronic component is not limited to a chip component such as a multilayer ceramic capacitor, but may be a composite component such as a circuit module, or an electronic substrate such as a circuit board or a multilayer board.
  • the electrode composed of the electrode layer is not limited to the external electrode, and may be any electrode. For example, it may be a pad electrode, a land electrode, a coiled electrode, or a circuit pattern electrode. That is, the electronic component of the present invention is not limited to electrodes such as external electrodes, and may be applied to circuits such as electronic substrates.
  • FIG. 2 is a side view schematically showing an example of a multilayer ceramic capacitor in which glass is present on the surface of an external electrode.
  • the multilayer ceramic capacitor 10 shown in FIG. 2 includes a rectangular parallelepiped or substantially rectangular parallelepiped ceramic body 11 and external electrodes 12 and 13 provided on both end faces of the ceramic body 11, respectively.
  • glass 14 is present on a part of the surfaces of the external electrodes 12 and 13, and a silicate film 15 is provided on the surface of the glass 14.
  • a plurality of internal electrodes 16 and 17 alternately drawn out on both end surfaces are provided inside the ceramic body 11.
  • the internal electrode 16 drawn out to one end face is connected to the external electrode 12, and the internal electrode 17 drawn out to the other end face is connected to the external electrode 13.
  • the ceramic body 11 is composed of, for example, a ceramic material containing a metal oxide containing titanium.
  • a metal oxide containing titanium examples include BaTIO 3 .
  • Each of the external electrodes 12 and 13 may be composed of one electrode layer or may be composed of a plurality of electrode layers.
  • the external electrodes 12 and 13 may be baked electrodes containing metal and glass, respectively, or may be resin electrodes containing metal and resin, respectively. Further, a plating electrode may be provided on the surface of the baking electrode or the resin electrode.
  • the external electrodes 12 and 13 wrap around to each part of the upper and lower surfaces of the ceramic element 11 in addition to the end surface of the ceramic element 11, but any surface of the ceramic element 11 can be used. It suffices if it is provided at the site.
  • FIG. 3 is a side view schematically showing an example of a multilayer ceramic capacitor in which glass is present at the interface between the external electrode and the ceramic element.
  • glass 14 is present on a part of the boundary surface between the external electrode 12 and the ceramic element 11 and a part of the boundary surface between the external electrode 13 and the ceramic element 11.
  • a silicate film 15 is provided on the surface of the glass 14.
  • the silicate film 15 is provided on the surface of the glass 14 which is not covered by the external electrodes 12 or 13.
  • FIG. 4 is a side view schematically showing an example of a multilayer ceramic capacitor in which glass is present on the surface of the ceramic body.
  • the glass 14 is present on a part of the surface of the ceramic element 11, and the silicate film 15 is provided on the surface of the glass 14.
  • FIG. 5 is a side view schematically showing another example of a multilayer ceramic capacitor in which glass is present on the surface of the ceramic body.
  • the glass 14 is present on the entire surface of the ceramic element 11, and the silicate film 15 is provided on the surface of the glass 14.
  • the glass 14 is present on the portion where the external electrode 12 and the internal electrode 16 are connected and the portion where the external electrode 13 and the internal electrode 17 are connected. Absent.
  • the silicate film 15 is also provided on the surface of the glass 14 covered by the external electrodes 12 or 13.
  • the electronic component of the present invention it is sufficient that the silicate film is provided on the outermost side of the electronic component. Therefore, the electronic component of the present invention includes a case where a silicate film is provided at a location as shown in FIG. 6 below.
  • FIG. 6 is an enlarged side view schematically showing an example of a multilayer ceramic capacitor in which glass is present on the surface of a ceramic body or an external electrode.
  • the glass 14A exists on the surfaces of the ceramic body 11 and the external electrode 12 at the portion where a part of the external electrode 12 is missing, and the silicate film 15A is provided on the surface of the glass 14A.
  • the glass 14B exists on the surface of a portion where a part of the external electrode 12 is recessed, and the silicate film 15B is provided on the surface of the glass 14B.
  • the silicate film 15B is not in contact with the external electrode 12 and is separated from it.
  • the glass 14C has cracks, and the silicate film 15C is provided on the surface of the cracks in the glass 14C.
  • the glass constituting the electronic component of the present invention contains at least one type of multivalent metal ion.
  • the polyvalent metal ion for example, at least one ion selected from the group consisting of Be, Mg, Ca, Sr, Ba, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga and Sn. And so on.
  • the glass constituting the electronic component of the present invention may further contain at least one monovalent metal ion.
  • the monovalent metal ion include at least one ion selected from the group consisting of Li, Na, K, Rb and Cs.
  • the type of glass constituting the electronic component of the present invention is not particularly limited, and examples thereof include borosilicate glass.
  • the silicate film constituting the electronic component of the present invention contains a multivalent metal ion common to glass.
  • the silicate film constituting the electronic component of the present invention is preferably formed by the [method for forming a silicate film] described later.
  • the silicate film since the silicate film is formed by the reaction of the polyvalent metal ion contained in the glass with the silicate ion, the silicate film contains the polyvalent metal ion derived from the glass.
  • examples of the polyvalent metal ions commonly contained in the glass and the silicate film include Be, Mg, Ca, Sr, Ba, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ga. And at least one ion selected from the group consisting of Sn and the like.
  • the content of the polyvalent metal ion contained in the silicate film is not particularly limited.
  • the silicate film constituting the electronic component of the present invention may further contain at least one monovalent metal ion.
  • the monovalent metal ion contained in the silicate film may or may not be common with glass.
  • the silicate film constituting the electronic component of the present invention may contain other glass components.
  • the silicate film may contain B (boron) ions.
  • the method for forming a silicate film of the present invention includes a step of applying a coating agent containing an alkali metal silicate to the surface of glass containing at least one polyvalent metal ion.
  • a coating agent containing an alkali metal silicate to the surface of glass containing at least one polyvalent metal ion.
  • polyvalent metal ions contained in glass are eluted on the surface of glass to form a silicate film containing polyvalent metal ions common to glass on the surface of glass. Will be done.
  • the method for forming a silicate film of the present invention is characterized in that a silicate film is formed on the surface of glass by utilizing elution of polyvalent metal ions.
  • the mechanism by which the silicate film is formed is that the negative charge of the silicate ion contained in the coating agent is neutralized by the positive charge of the polyvalent metal ion eluted from the surface of the glass, so that the negative charge is lost. It is possible that it will precipitate. Further, since the activity of water on the surface of the glass decreases due to the elution of polyvalent metal ions from the surface of the glass, it is conceivable that the silicate ions contained in the coating agent are salted out.
  • silicate film By forming the silicate film on the surface of the glass by the above method, it is possible to suppress the elution of glass components such as polyvalent metal ions into water or an aqueous solution. As a result, a dense glass is maintained.
  • the silicate film is formed on the portion where the polyvalent metal ion is eluted, the silicate film is uniformly formed even if the shape of the glass is complicated. Therefore, the silicate film can be uniformly formed regardless of the shape of the object.
  • the method for forming a silicate film of the present invention may be applied when glass is present on a part of the surface of an object. In this case, even if the coating agent is applied to the entire surface of the object, the silicate film can be selectively formed only on the surface of the glass from which the polyvalent metal ions are eluted.
  • the method for forming a silicate film of the present invention further comprises a step of preparing an electronic component including a ceramic body and an electrode layer provided on a part of the surface of the ceramic body, and the glass is ,
  • the ceramic body and the electrode layer may be present on at least one surface.
  • the elution of the glass component is suppressed to suppress the deterioration of the moisture resistance reliability of the electronic component described in [Problems to be Solved by the Invention]. can do.
  • the coating agent may be applied to the surface of the electronic component in the step of applying the coating agent.
  • the silicate film is selectively formed only on the surface of the glass among the surfaces of the electronic component. Therefore, even when the surface of the electrode layer is plated, the silicate film does not hinder the plating treatment, so that good plating properties can be obtained.
  • the glass used in the method for forming a silicate film of the present invention contains at least one polyvalent metal ion.
  • the polyvalent metal ion for example, at least one ion selected from the group consisting of Be, Mg, Ca, Sr, Ba, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga and Sn. And so on.
  • the glass used in the method for forming a silicate film of the present invention may further contain at least one monovalent metal ion.
  • the monovalent metal ion include at least one ion selected from the group consisting of Li, Na, K, Rb and Cs.
  • the type of glass used in the method for forming a silicate film of the present invention is not particularly limited, and examples thereof include borosilicate glass.
  • the coating agent used in the method for forming a silicate film of the present invention contains an alkali metal silicate.
  • the alkali metal silicate for example, a water glass-based material such as lithium silicate, sodium silicate, and potassium silicate can be used.
  • reagents such as lithium silicate, sodium silicate, and potassium silicate may be used, and other water-soluble alkali metal silicates may be used.
  • a lithium silicate solution commercially available from Nissan Chemical Industries, Ltd., Nippon Chemical Industrial Co., Ltd., etc. can be used.
  • the content of the alkali metal silicate in the coating agent is, for example, 0.1% by weight or more and 50% by weight or less.
  • the content of the alkali metal silicate in the coating agent is preferably 0.1% by weight or more.
  • the coating agent further contains a solvent.
  • the coating agent preferably contains an inorganic solvent, and more preferably contains an inorganic solvent and an organic solvent.
  • the inorganic solvent examples include water.
  • the content of the inorganic solvent in the coating agent is, for example, 50% by weight or more and 99.9% by weight or less.
  • the organic solvent examples include water-soluble organic solvents such as alcohols and glycols.
  • the content of the organic solvent in the coating agent is, for example, 1% by weight or more and 30% by weight or less. As the amount of the organic solvent increases, the alkali metal silicate becomes less soluble in the coating agent. Therefore, the content of the organic solvent in the coating agent is preferably 30% by weight or less.
  • the coating agent may contain a surface conditioner, a coupling agent, a glass etching agent, a silicate curing catalyst, a filler and the like as additives.
  • the coating agent may contain an additive, the additive may be only one type or two or more types.
  • the surface conditioner is used to reduce the surface tension of the coating agent.
  • the surface conditioner include aqueous silicones, alcohols, glycols and the like.
  • the content of the surface adjusting agent in the coating agent is, for example, 0.01% by weight or more and 20% by weight or less.
  • the alkali metal silicate becomes less soluble in the coating agent, so that the content of the surface conditioner in the coating agent is preferably 20% by weight or less.
  • the coupling agent is used to adjust the surface tension of the coating agent.
  • the content of the coupling agent in the coating agent is, for example, 0.01% by weight or more and 5% by weight or less.
  • glass etching agent examples include fluoride ions and various complexing agents.
  • specific examples of the complexing agent include ethylenediamine, ethylenediaminetetraacetic acid, citric acid, oxalic acid, tartaric acid, thiourea, ammonia, acetic acid, lactic acid, malic acid, maleic acid, fumaric acid, glycols, and polyhydric alcohol. Be done.
  • the acid may be H-type or sodium, potassium salt or the like as long as it is water-soluble, but polyvalent metal salts are not preferable because they precipitate silicic acid and insoluble salts.
  • the content of the glass etching agent in the coating agent is, for example, 1 ppm or more and 10,000 ppm or less. As the amount of the glass etching agent increases, the glass component tends to elute during the formation of the silicate film. Therefore, the content of the glass etching agent in the coating agent is preferably 10,000 ppm or less.
  • the curing catalyst for silicate examples include phosphoric acid, polyhydric alcohol, and polyvalent transition metal.
  • Specific examples of the silicate curing catalyst include pyrophosphoric acid, glioxal, zinc chloride, copper chloride, iron chloride, aluminum chloride and the like.
  • the acid may be H-type or sodium, potassium salt or the like as long as it is water-soluble, but polyvalent metal salts are not preferable because they precipitate silicic acid and insoluble salts.
  • an anionic species such as sulfate, chloride salt, and carbonate can be selected as long as it is water-soluble, but it is not preferable because a large amount of the metal ion precipitates a silicate and an insoluble salt.
  • the content of the silicate curing catalyst in the coating agent is, for example, 1 ppm or more and 10,000 ppm or less. As the amount of the silicate curing catalyst increases, the storage stability (pot life) of the coating agent tends to decrease. Therefore, the content of the silicate curing catalyst in the coating agent is preferably 10,000 ppm or less.
  • the filler is preferably one that can be dispersed in water and does not dissolve under the alkali of the aqueous silicate solution.
  • a filler examples include nanofillers such as zirconia and alumina.
  • the coating agent contains a filler
  • the content of the filler in the coating agent is, for example, 1 ppm or more and 200,000 ppm or less. Since the film strength tends to decrease as the amount of the filler increases, the content of the filler in the coating agent is preferably 200,000 ppm or less.
  • various methods such as dipping, spray coating, printing, and spin coating can be used as a method for applying a coating agent to the surface of glass.
  • the coating agent In order to form the silicate film, the coating agent needs to be a liquid and has a viscosity low to some extent (for example, 1 Pa ⁇ s or less). Therefore, the treatment temperature for forming the silicate film is preferably a temperature from room temperature until the coating agent boils, for example, room temperature. The lower the treatment temperature, the more easily the reactivity decreases, and the higher the treatment temperature, the more easily the storage stability (pot life) of the coating agent decreases. In the present specification, the room temperature means a temperature range defined in JIS Z 8703, and specifically means a temperature range of 5 ° C. or higher and 35 ° C. or lower.
  • the treatment time for forming the silicate film is preferably 5 seconds or more and 24 hours or less, for example, 1 minute.
  • the surface tension of the coating agent is preferably 10 mN / m or more and 72 mN / m or less.
  • the pH of the coating agent is preferably 10 or more and 12.5 or less.
  • the method for forming a silicate film of the present invention preferably further includes a cleaning step after the silicate film is formed on the surface of the glass. Excess coating agent and the like can be washed off by the washing step.
  • the method for forming a silicate film of the present invention may further include a drying step after the washing step. Moisture can be removed by the drying step.
  • a silicate film containing polyvalent metal ions common to glass is formed on the surface of glass. That is, the surface-modified glass of the present invention can be produced by the method for forming a silicate film of the present invention. Further, by applying the method for forming a silicate film of the present invention to an electronic component, the electronic component of the present invention can be manufactured.
  • silicate film formed by the method for forming the silicate film of the present invention has the same structure as the silicate film described in [Surface modified glass], detailed description thereof will be omitted.
  • Example 1 A coating agent containing a lithium silicate solution: 25% by weight and water: the rest was prepared. A glass substrate of about 1 cm square composed of borosilicate glass was prepared and immersed in the coating agent at room temperature for 1 minute. Then, the glass substrate was washed with water and dried to prepare a sample of Example 1.
  • Comparative Example 1 Similar to Example 1, a glass substrate of about 1 cm square composed of borosilicate glass was prepared. Unlike Example 1, the glass substrate was not immersed in the coating agent and was used as it was as the sample of Comparative Example 1.
  • Example 1 The samples of Example 1 and Comparative Example 1 were immersed in pure water at room temperature for 15 minutes. The amount of Al, B, Ba and Ca contained in the borosilicate glass eluted in pure water was quantified by inductively coupled plasma (ICP) emission spectrometry. The results are shown in Table 1.
  • ICP inductively coupled plasma
  • Example 1 From Table 1, it can be seen that in Example 1, the elution of the glass component was suppressed as compared with Comparative Example 1. It is considered that this is because a silicate film was formed on the surface of the glass by immersing the glass substrate in the coating agent.
  • Example 2 A monolithic ceramic capacitor was produced by forming a baking electrode containing copper and borosilicate glass as an external electrode with respect to a ceramic element using BaTiO 3 as a base material. The obtained multilayer ceramic capacitor was immersed in the coating agent used in Example 1 at room temperature for 1 minute. Then, the multilayer ceramic capacitor was washed with water and dried to prepare a sample of Example 2.
  • the external electrodes formed on the sample of Example 2 were TEM-observed by the following method.
  • a cross-sectional sample of the surface of the external electrode was taken out by focused ion beam (FIB) processing, and TEM observation was performed with a TEM (JEM-2200FS manufactured by JEOL Ltd.).
  • FIB focused ion beam
  • JEM-2200FS manufactured by JEOL Ltd.
  • the surface of the external electrode was subjected to Pt sputtering and carbon deposition before FIB processing.
  • FIG. 7 is a TEM image showing a part of the external electrode formed on the sample of Example 2.
  • FIG. 8 is an enlarged TEM image of the portion surrounded by the broken line in FIG. 7. As shown in FIGS. 7 and 8, it can be confirmed that a film is formed on the surface of the glass, whereas no film is formed on the surface of the copper.
  • a line analysis by EDX was performed from X to Y in FIG. 8 using the same device as the TEM observation.
  • the spot diameter was 1.0 nm, and the number of integrations was 100.
  • FIG. 9 is a graph showing the composition of the film and glass constituting the sample of Example 2. From FIG. 9, it can be seen that the film contains elements of multivalent metal ions common to glass, and that the content of each element gradually changes across the boundary between the film and glass. You can check. Since the film contains Si, it can be seen that a silicate film is formed on the surface of the glass.
  • the content of Ca and Ba contained in the film located at the interface with the glass is contained in the glass located at the interface with the film. It is less than the content of Ca and Ba.
  • the content of Al, Cu and Zn contained in the film located at the interface with the glass is contained in the glass located at the interface with the film. It is higher than the content of Al, Cu and Zn.
  • Example 3 A coating agent containing lithium silicate as an alkali metal silicate: 6% by weight and water as an inorganic solvent: 94% by weight was prepared. The viscosity, surface tension and pH of the coating agent were measured. The viscosity of the coating agent was measured using a viscometer (manufactured by A & D, SV-10). The surface tension of the coating agent was measured using a drip meter (manufactured by Mutual Physical and Chemical Glass Manufacturing Co., Ltd., JIS K-3362 compliant). The pH of the coating agent was measured using a pH meter (manufactured by HORIBA, Ltd., using 6637-10D as a pH electrode).
  • a 10 mm square glass substrate was prepared and immersed in the above coating agent at 25 ° C. for 1 minute. Then, the glass substrate was washed with water and dried at 65 ° C. for 1 hour to prepare a sample of Example 3.
  • Example 4 A sample of Example 4 was prepared in the same manner as in Example 3 except that the time for allowing the glass substrate to be immersed in the coating agent was changed to 5 minutes.
  • Example 5 A sample of Example 5 was prepared in the same manner as in Example 3 except that the time for allowing the glass substrate to be immersed in the coating agent was changed to 15 minutes.
  • Example 6 A sample of Example 6 was prepared in the same manner as in Example 3 except that the time for allowing the glass substrate to be immersed in the coating agent was changed to 30 minutes.
  • Example 7 A sample of Example 7 was prepared in the same manner as in Example 4 except that the temperature at which the glass substrate was statically immersed in the coating agent was changed to 15 ° C.
  • Example 8 A sample of Example 8 was prepared in the same manner as in Example 4 except that the temperature at which the glass substrate was statically immersed in the coating agent was changed to 35 ° C.
  • Example 9 in the same manner as in Example 4 except that a coating agent containing lithium silicate as an alkali metal silicate: 1.2% by weight and water as an inorganic solvent: 98.8% by weight was prepared. Samples were prepared.
  • Example 10 A sample of Example 10 was prepared in the same manner as in Example 4 except that a coating agent containing lithium silicate as an alkali metal silicate: 3% by weight and water as an inorganic solvent: 97% by weight was prepared. did.
  • Example 11 A sample of Example 11 was prepared in the same manner as in Example 4 except that a coating agent containing lithium silicate as an alkali metal silicate: 12% by weight and water as an inorganic solvent: 88% by weight was prepared. did.
  • Example 12 A sample of Example 12 was prepared in the same manner as in Example 4 except that a coating agent containing lithium silicate as an alkali metal silicate: 18% by weight and water as an inorganic solvent: 82% by weight was prepared. did.
  • Example 13 The same as in Example 4 except that a coating agent containing lithium silicate as an alkali metal silicate: 12% by weight, butanol as an organic solvent: 3% by weight, and water as an inorganic solvent: the rest was prepared. , A sample of Example 13 was prepared.
  • Example 14 Lithium silicate as alkali metal silicate: 12% by weight, ethylenediamine tetraacetic acid (EDTA) as glass etching agent: 3,000 ppm, water as inorganic solvent: except that a coating agent containing the rest was prepared.
  • EDTA ethylenediamine tetraacetic acid
  • a sample of Example 14 was prepared in the same manner as in Example 4.
  • Example 15 Examples except that a coating agent containing lithium silicate as an alkali metal silicate: 12% by weight, pyrophosphate as a curing catalyst for the silicate: 3,000 ppm, and water as an inorganic solvent: the rest was prepared. A sample of Example 15 was prepared in the same manner as in 4.
  • Example 16 Lithium silicate as alkali metal silicate: 12% by weight, silica as filler (Nissan Chemical Industries, Ltd., Snowtex (registered trademark) ST-UP): 10,000 ppm, water as inorganic solvent: including the rest A sample of Example 16 was prepared in the same manner as in Example 4 except that a coating agent was prepared.
  • Example 17 Lithium silicate as alkali metal silicate: 12% by weight, butanol as an organic solvent: 3% by weight, ethylenediamine tetraacetic acid (EDTA) as a glass etching agent: 3,000 ppm, as a curing catalyst for silicate. Pyrrolic acid: 3,000 ppm, silica as filler (Nissan Chemical Co., Ltd., Snowtex (registered trademark) ST-UP): 10,000 ppm, water as an inorganic solvent: except that a coating agent containing the rest was prepared. , A sample of Example 17 was prepared in the same manner as in Example 4.
  • Comparative Example 2 A 10 mm square glass substrate was prepared in the same manner as in Example 3. Unlike Example 3, the glass substrate was not subjected to the treatment of allowing it to be immersed in the coating agent, and was used as it was as the sample of Comparative Example 2.
  • Example 3 to 17 and Comparative Example 2 were immersed in 10 g of pure water and allowed to stand in an oven at 60 ° C. for 2 hours. Then, the sample was taken out, and the amount [mmol] of the glass component eluted in pure water was quantified by ICP emission analysis. Further, for Examples 3 to 17, in order to evaluate the effect of suppressing the elution amount of the glass component, the ratio of the elution amount in Examples 3 to 17 to the elution amount in Comparative Example 2 was determined. The results are shown in Table 2.

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