WO2022017023A1 - 无铅玻璃浆料、贴片电阻及其制备方法 - Google Patents

无铅玻璃浆料、贴片电阻及其制备方法 Download PDF

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Publication number
WO2022017023A1
WO2022017023A1 PCT/CN2021/098826 CN2021098826W WO2022017023A1 WO 2022017023 A1 WO2022017023 A1 WO 2022017023A1 CN 2021098826 W CN2021098826 W CN 2021098826W WO 2022017023 A1 WO2022017023 A1 WO 2022017023A1
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lead
free glass
glass paste
parts
solvent
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PCT/CN2021/098826
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English (en)
French (fr)
Inventor
沈宏坤
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Changxin Memory Technologies Inc
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Changxin Memory Technologies Inc
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Priority to US17/487,666 priority Critical patent/US11802076B2/en
Publication of WO2022017023A1 publication Critical patent/WO2022017023A1/zh
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    • 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
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • C09D185/04—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers containing boron
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/02—Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/02—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the application belongs to the technical field of packaging materials, and in particular relates to a lead-free glass paste, a chip resistor and a preparation method thereof.
  • glass paste is generally used to prepare the protective layer, and the existing glass paste will contain a large amount of lead oxide.
  • the lead in the lead-containing glass paste will cause environmental pollution, so the industry, customers and regulations are all committed to the lead-free chip resistors.
  • the lead content in the glass paste is generally reduced by replacing lead oxide or the lead-free glass paste is realized.
  • the existing lead-free glass pastes have the problem of poor high temperature resistance, and the patch The resistor will generate a lot of heat during operation, and the existing lead-free glass paste cannot meet the needs of the chip resistor.
  • a lead-free glass paste, a chip resistor and a method for preparing the same are provided.
  • the present application provides a lead-free glass paste, which, in parts by mass, comprises the following components: 6-7 parts of borosilicate oil, 12-21 parts of alumina powder, 2-3 parts of glass fiber powder and 0.1-0.5 part of curing agent .
  • the lead-free glass paste in the above embodiment is lead-free glass paste, which not only meets the requirements of environmental protection, but also has good thermal stability, and the heat-resistant temperature can reach above 640°C.
  • the borosilicone oil in parts by mass, includes the following components: 100-115 parts of phenyl silicon-containing substances, 13-28 parts of boron-containing monomers, 50-75 parts of silane, and 60 parts of dihydroxypyridine ⁇ 80 servings.
  • the phenylsilicon-containing substance includes: at least one of ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenylsilicon diol;
  • the silane includes: two At least one of chlorodimethylsilane, dichlorodiethylsilane and dichlorodiphenylsilane;
  • the dihydroxypyridines include: 2,4-dihydroxypyridine, 2,6-dihydroxypyridine and 3,5 -At least one of dihydroxypyridine;
  • the boron-containing monomer includes at least one of boric acid, phenylboronic acid, triisopropyl borate and dichlorophenylborane.
  • the alumina powder includes at least one of nanoscale alumina powder, fumed alumina powder and ⁇ -type nanoscale alumina powder.
  • the glass fiber powder includes at least one of alkali-free glass fiber powder, alkali-resistant glass fiber powder, high-alkali glass fiber powder, and medium-alkali glass fiber powder.
  • the curing agent includes at least one of TMO, bis-25, dibutyltin dilaurate, dibutyltin diacetate, and DCP.
  • the chemical structural formula of the lead-free glass paste is:
  • x:y 1.1-1.9:0.3-0.7;
  • R 1 is phenyl, hydroxyl or ethanol;
  • R 2 is methyl, ethyl or phenyl;
  • R 3 is dihydroxypyridine.
  • the present application also provides a method for preparing lead-free glass paste as described in any of the above embodiments, comprising:
  • a curing agent is added to the mixture for curing and then crushed to obtain the lead-free glass paste.
  • the lead-free glass paste prepared in the above embodiment is lead-free glass paste, which not only meets the environmental protection requirements, but also has good thermal stability, and the heat-resistant temperature can reach above 640°C.
  • preparing borosilicone oil includes:
  • the weight of the phenyl silicon-containing substance is 100g-115g
  • the weight of the boron-containing monomer is 13g-28g
  • the volume of the first solvent is 150ml ⁇ 250ml
  • the first solvent includes dichloroethane solvent
  • the weight of the silane is 50g-75g
  • the weight of the dihydroxypyridine is 60g-80g
  • the volume of the second solvent is 350ml to 450ml
  • the second solvent includes propyl acetate solvent
  • the weight part of the first product is 1 part to 1.1 part
  • the weight part of the second product is 0.95 part to 1 part
  • the volume of the third solvent ranges from 95ml to 150ml
  • the third solvent includes acetone.
  • the reaction temperature in the process of obtaining the first product is 50°C to 75°C, and the reaction time is 2.5h to 3.5h; the reaction temperature in the process of obtaining the second product is 60°C ⁇ 90°C, the reaction time is 1.5h-2.5h; the reaction temperature in the process of obtaining the borosilicate oil is 35°C-45°C, and the reaction time is 5.5h-6.5h.
  • the temperature of the curing reaction is 26° C. ⁇ 45° C.
  • the time of the curing reaction is 5 h ⁇ 7 h.
  • the application also provides a chip resistor, including:
  • a bottom electrode located on the lower surface of the substrate
  • an upper electrode one end is in contact with the bottom electrode, and the other end extends from the sidewall of the substrate to the upper surface of the substrate;
  • a barrier layer located on the surface of the upper electrode away from the substrate;
  • an external electrode located on the surface of the barrier layer away from the upper electrode
  • a resistance layer located on the upper surface of the substrate and on one side of the upper electrode
  • the first protective layer is prepared from the lead-free glass paste as described in any of the listed examples.
  • the second protective layer is located on the upper surface of the first protective layer.
  • the lead-free glass paste in any of the above embodiments is used to prepare the first protective layer, which not only meets the environmental protection requirements, but also has good thermal stability, and the temperature resistance temperature can reach above 640°C.
  • the present application also provides a method for preparing a chip resistor, comprising:
  • an upper electrode forming an upper electrode, a barrier layer and an external electrode; wherein, one end of the upper electrode is in contact with the bottom electrode, and the other end extends to the upper surface of the substrate through the sidewall of the substrate; the barrier layer is located on the The upper electrode is far from the surface of the substrate; the external electrode is located on the surface of the barrier layer far away from the upper electrode;
  • the resistance layer is located on one side of the upper electrode
  • the lead-free glass paste is prepared by using the preparation method of the lead-free glass paste as described in any of the above embodiments;
  • a second protective layer is formed on the upper surface of the first protective layer.
  • the lead-free glass paste prepared by the preparation method of the lead-free glass paste in any of the above-mentioned embodiments is used to prepare the first protective layer, which not only meets the environmental protection requirements, but also has better performance.
  • Thermal stability, temperature resistance temperature can reach above 640 °C.
  • FIG. 1 is a flowchart of a method for preparing lead-free glass paste provided in an embodiment of the present application.
  • FIG. 2 is a flow chart of preparing borosilicate oil in the preparation method of lead-free glass paste provided in an embodiment of the application.
  • FIG. 3 is a schematic cross-sectional structure diagram of a chip resistor provided in another embodiment of the present application.
  • FIG. 4 is a flowchart of a method for fabricating a chip resistor provided in yet another embodiment of the present application.
  • the present application provides a lead-free glass paste, which, in parts by mass, comprises the following components: 6-7 parts of borosilicate oil, 12-21 parts of alumina powder, 2-3 parts of glass fiber powder and 0.1-0.5 part of curing agent .
  • the lead-free glass paste in the above embodiment is lead-free glass paste, which meets environmental protection requirements, and the lead-free glass paste has good thermal stability, and the heat-resistant temperature can reach above 640°C.
  • the lead-free glass paste may include the following components in parts by mass: 6.2-6.8 parts of borosilicate oil, specifically, 6.2 parts, 6.5 parts or 6.8 parts of borosilicate oil; 15-18 parts of alumina powder 15 parts, 16 parts, 17 parts or 18 parts of silicon oxide powder; 2.2-2.8 parts of glass fiber powder, specifically, 2.2 parts, 2.5 parts or 2.8 parts of glass fiber powder; and curing agent 0.2 to 0.4 part, specifically, the curing agent may be 0.2 part, 0.3 part or 0.4 part.
  • the borosilicone oil may include the following components: 100-115 parts of phenyl silicon-containing substances, 13-28 parts of boron-containing monomers, 50-75 parts of silane, and 60-80 parts of dihydroxypyridine
  • the silicon-containing material can be 100 parts, 105 parts, 110 parts or 115 parts
  • the boron-containing monomer can be 13 parts, 15 parts, 20 parts, 25 parts or 28 parts
  • the silane can be 13 parts, 15 parts, 20 parts, 25 parts or 28 parts.
  • the dihydroxypyridine can be 60 parts, 65 parts, 70 parts, 75 parts or 80 parts.
  • the phenylsilicon-containing substance includes: at least one of ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenylsilicon diol, that is, the phenylsilicon-containing substance may include Any one of ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenylsilicon diol, and may be ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenyldimethoxysilane. Any two or a combination of two or more of the phenylsilicon diols.
  • the silane includes: at least one of dichlorodimethylsilane, dichlorodiethylsilane and dichlorodiphenylsilane, that is, the silane may be dichlorodimethylsilane, dichlorodiethylsilane and any one of dichlorodiphenylsilane, and may be any two or a combination of two or more of dichlorodimethylsilane, dichlorodiethylsilane, and dichlorodiphenylsilane.
  • the dihydroxypyridine includes: at least one of 2,4-dihydroxypyridine, 2,6-dihydroxypyridine and 3,5-dihydroxypyridine, that is, the dihydroxypyridine may be 2,4-dihydroxypyridine Any of hydroxypyridine, 2,6-dihydroxypyridine and 3,5-dihydroxypyridine, and may be 2,4-dihydroxypyridine, 2,6-dihydroxypyridine and 3,5-dihydroxypyridine Any two or a combination of two or more of them.
  • the boron-containing monomer includes at least one of boric acid, phenylboronic acid, triisopropyl borate, and dichlorophenylborane, that is, the boron-containing monomer may be boric acid, phenylboronic acid, triisopropyl borate, and dichlorophenylborane.
  • the boron-containing monomer may be boric acid, phenylboronic acid, triisopropyl borate, and dichlorophenylborane.
  • Any one of chlorophenylborane may be any two or a combination of two or more of boric acid, phenylboronic acid, triisopropyl borate and dichlorophenylborane.
  • the alumina powder includes at least one of nanoscale alumina powder, fumed alumina powder and ⁇ -type nanoscale alumina powder; that is, the alumina powder may be nanoscale alumina powder, fumed alumina powder and any one of the ⁇ -type nanoscale alumina powders, or any two or a combination of two or more of the nanoscale alumina powders, fumed alumina powders, and ⁇ -type nanoscale alumina powders.
  • the glass fiber powder includes at least one of alkali-free glass fiber powder, alkali-resistant glass fiber powder, high-alkali glass fiber powder, and medium-alkali glass fiber powder; that is, the glass fiber powder may be alkali-free glass fiber powder , any one of alkali-resistant glass fiber powder, high-alkali glass fiber powder and medium-alkali glass fiber powder, and can also be alkali-free glass fiber powder, alkali-resistant glass fiber powder, high-alkali glass fiber powder and medium-alkali glass fiber powder Any two or a combination of two or more of them.
  • the curing agent includes TMO (tetramethoxysilane), bis-25 (2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane), dibutyltin dilaurate , at least one in dibutyltin diacetate and DCP (dicumyl peroxide); that is, curing agent can be any one in TMO, two 25, dibutyltin dilaurate, dibutyltin diacetate and DCP, also It can be any two or a combination of two or more of TMO, bis-25, dibutyltin dilaurate, dibutyltin diacetate and DCP.
  • TMO tetramethoxysilane
  • bis-25 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane
  • dibutyltin dilaurate at least one in dibutyltin diacetate and DCP (dicumyl peroxide
  • the chemical formula of the lead-free glass paste can be:
  • x:y 1.1-1.9:0.3-0.7;
  • R 1 is phenyl, hydroxyl or ethanol;
  • R 2 is methyl, ethyl or phenyl;
  • R 3 is dihydroxypyridine.
  • the present application further provides a method for preparing lead-free glass paste as described in any of the above solutions, including:
  • step S11 may include the following steps:
  • the weight of the weighed phenyl silicon-containing substance may be 100g ⁇ 115g, for example, 100g, 105g, 110g or 115g, etc.; the weight of the weighed boron-containing monomer may be 13g ⁇ 115g 28g, for example, 13g, 15g, 20g, 25g or 28g, etc.; the first solvent may include dichloroethane solvent, and the volume of the first solvent may be 150ml to 200ml, for example, 150ml, 160ml, 170ml, 180ml, 190ml or 200ml.
  • the weight of the weighed silane may be 50g-75g, for example, 50g, 55g, 60g, 65g, 70g or 75g, etc.; the weight of the weighed dihydroxypyridine may be 60g ⁇ 80g, for example, can be 60g, 65g, 70g, 75g, 80g, etc.; the second solvent can include propyl acetate solvent, and the volume of the second solvent can be 350ml ⁇ 450ml, for example, can be 350ml, 400ml or 450ml etc.
  • the weight part of the first product can be 1 part to 1.1 part, for example, it can be 1 part, 1.01 part, 1.05 part or 1.1 part, etc.; the weighed second product
  • the mass part of the solvent can be 0.95 part-1 part, for example, it can be 0.95 part or 1 part, etc.;
  • the third solvent can include acetone, and the volume of the third solvent can be 95ml-150ml, for example, can be 95ml, 100ml, 110ml , 120ml, 130ml, 140ml or 150ml and so on.
  • step S111 the first solvent is removed under low pressure (lower than normal pressure) after the reaction;
  • the reaction temperature in step S111 may be 50°C to 75°C, and the reaction time may be 2.5h to 3.5h;
  • the reaction temperature in this step can be 50°C, 60°C, 70°C or 75°C, etc.; the reaction time can be 2.5h, 3h or 3.5h and the like.
  • step S112 the second solvent is removed under low pressure; the reaction temperature in step S112 may be 60°C to 90°C, and the reaction time may be 1.5h to 2.5h; specifically, the reaction temperature of this step It can be 60°C, 70°C, 80°C or 90°C and so on, and the reaction time can be 1.5h, 2h or 2.5h and so on.
  • the reaction temperature may be 35°C to 45°C, and the reaction time may be 5.5h to 6.5h; specifically, the reaction temperature may be 35°C, 40°C, or 45°C, etc., and the reaction time may be 5.5h, 6h or 6.5h and so on.
  • the phenylsilicon-containing substance includes: at least one of ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenylsilicon diol, that is, the phenylsilicon-containing substance may include Any one of ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenylsilicon diol, and may be ethoxydiphenylsilane, diphenyldimethoxysilane, and diphenyldimethoxysilane. Any two or a combination of two or more of the phenylsilicon diols.
  • the silane includes: at least one of dichlorodimethylsilane, dichlorodiethylsilane and dichlorodiphenylsilane, that is, the silane may be dichlorodimethylsilane, dichlorodiethylsilane and any one of dichlorodiphenylsilane, and may be any two or a combination of two or more of dichlorodimethylsilane, dichlorodiethylsilane, and dichlorodiphenylsilane.
  • the dihydroxypyridine includes: at least one of 2,4-dihydroxypyridine, 2,6-dihydroxypyridine and 3,5-dihydroxypyridine, that is, the dihydroxypyridine may be 2,4-dihydroxypyridine Any of hydroxypyridine, 2,6-dihydroxypyridine and 3,5-dihydroxypyridine, and may be 2,4-dihydroxypyridine, 2,6-dihydroxypyridine and 3,5-dihydroxypyridine Any two or a combination of two or more of them.
  • the boron-containing monomer includes at least one of boric acid, phenylboronic acid, triisopropyl borate, and dichlorophenylborane, that is, the boron-containing monomer may be boric acid, phenylboronic acid, triisopropyl borate, and dichlorophenylborane.
  • the boron-containing monomer may be boric acid, phenylboronic acid, triisopropyl borate, and dichlorophenylborane.
  • Any one of chlorophenylborane may be any two or a combination of two or more of boric acid, phenylboronic acid, triisopropyl borate and dichlorophenylborane.
  • step S12 in parts by mass, weigh 6-7 parts of the borosilicate oil prepared in step S1, weigh 12-21 parts of alumina powder, and weigh 2-3 parts of glass fiber powder , Mix the weighed borosilicone oil and alumina powder, namely glass fiber powder evenly; It is 12 parts, 15 parts or 21 parts, etc., and the weight part of the stripped fiber powder can be 2 parts, 2.5 parts or 3 parts and so on.
  • the alumina powder includes at least one of nanoscale alumina powder, fumed alumina powder and ⁇ -type nanoscale alumina powder; that is, the alumina powder may be nanoscale alumina powder, fumed alumina powder and any one of the ⁇ -type nanoscale alumina powders, or any two or a combination of two or more of the nanoscale alumina powders, fumed alumina powders, and ⁇ -type nanoscale alumina powders.
  • the glass fiber powder includes at least one of alkali-free glass fiber powder, alkali-resistant glass fiber powder, high-alkali glass fiber powder, and medium-alkali glass fiber powder; that is, the glass fiber powder may be alkali-free glass fiber powder , any one of alkali-resistant glass fiber powder, high-alkali glass fiber powder and medium-alkali glass fiber powder, and can also be alkali-free glass fiber powder, alkali-resistant glass fiber powder, high-alkali glass fiber powder and medium-alkali glass fiber powder Any two or a combination of two or more of them.
  • a curing agent is added to the mixture obtained in step S2, and the added curing agent may be 0.1 to 0.5 parts by mass, stir evenly, remove air bubbles at low pressure, and cure at a preset temperature
  • the reaction product is obtained by reacting for a certain period of time; specifically, the mass part of the added curing agent may be 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part.
  • the temperature of the curing reaction can be 26°C to 45°C, for example, 26°C, 30°C, 35°C, 40°C, or 45°C, etc.; the time of the curing reaction can be 5h to 7h, for example, 5h, 6h or 7h.
  • step S13 any kind of crushing process can be used to crush the obtained reaction product to obtain lead-free glass paste.
  • the curing agent includes at least one of TMO, bis-25, dibutyltin dilaurate, dibutyltin diacetate and DCP; that is, the curing agent may be TMO, bis-25, dibutyltin dilaurate, diacetic acid Any one of dibutyltin and DCP may be any two or a combination of two or more of TMO, bis-25, dibutyltin dilaurate, dibutyltin diacetate and DCP.
  • the lead-free glass paste prepared in the above embodiment is lead-free glass paste, which meets environmental protection requirements, and the lead-free glass paste has good thermal stability, and the heat resistance temperature can reach above 640°C.
  • Step 1 Add 26 g of dichlorophenylborane to the beaker, dissolve it in 200 mL of dichloroethane, add it to a 500 mL four-necked flask after dissolving, add 100 g of diethoxydiphenylsilane, pass nitrogen, Under the atmosphere, the temperature was raised to 55°C, mechanically stirred, and the rotating speed was 500 r/min. After stirring for 3 hours, the pressure was reduced to -0.05 MPa, and the gauge pressure of the vacuum pump was -0.05 MPa.
  • the solvent was removed to obtain the first product A; 70 g of dichlorodimethylsilane was weighed and dissolved Dissolve 400 mL of propyl acetate into a 1000 mL four-necked flask, add 75 g of 2,6-dihydroxypyridine, pass nitrogen, heat up to 66°C under nitrogen atmosphere, stir mechanically, rotate at 500 r/min, stir After 2 hours of reaction, the pressure was reduced to a vacuum pump gauge pressure of -0.05MPa, and the solvent was removed to obtain the second product B; 1.01 parts of the first product A and 1 part of the second product B were taken, dissolved in 100 mL of acetone, and 250 mL was added after dissolving. In the four-necked flask, react at 40 °C for 6 h to obtain special borosilicate oil;
  • Step 2 Weigh 6.2 parts of borosilicate oil, add 16 parts of ⁇ -type nano-alumina powder, add alkali-free glass fiber powder, and mix to obtain a mixture;
  • Step 3 Add curing agent Shuang 25 to the mixture, stir evenly, remove air bubbles at low pressure, react at 35° C. for 6 hours to obtain a product, and use a crusher to crush the product to obtain glass slurry.
  • the heat resistance of the glass paste prepared in Example 1 reached 689°C.
  • the present application also provides a chip resistor, comprising: a substrate 1; a bottom electrode 2, the bottom electrode 2 is located on the lower surface of the substrate 1; an upper electrode 3, one end of the upper electrode 3 is connected to The bottom electrode 2 is in contact, and the other end extends from the side wall of the substrate 1 to the upper surface of the substrate 1; the barrier layer 4, the barrier layer 4 is located on the surface of the upper electrode 3 away from the substrate 1; the outer electrode 5, the outer electrode 5 is located in the barrier layer 4 away from the surface of the upper electrode 3; the resistance layer 6, the resistance layer 6 is located on the upper surface of the substrate 1, and the resistance layer 6 is located on one side of the upper electrode 3; the first protective layer 7, the first protective layer 7 is located on the resistance layer 6 surface; the first protective layer 7 can be prepared from the lead-free glass paste as in any of the above-mentioned embodiments.
  • the specific components and characteristics of the lead-free glass paste please refer to the above-mentioned embodiments, which will be prepared from the lead-free glass paste as
  • the lead-free glass paste in any of the above embodiments is used to prepare the first protective layer 7, which not only meets the requirements of environmental protection, but also has good thermal stability, and the temperature resistance temperature can reach above 640°C .
  • the substrate 1 may include, but is not limited to, an alumina substrate; the bottom electrode 2 may include, but is not limited to, a silver electrode; the upper electrode 3 may include, but is not limited to, a silver electrode, a palladium electrode, or a mixed electrode of silver and palladium; the barrier layer 4 Can include but not limited to nickel layer; external electrode 5 can include but not limited to tin electrode; resistance layer 6 can include but not limited to ruthenium oxide layer; second protective layer 8 can include but not limited to epoxy resin layer.
  • a section of the upper electrode 3 , the isolation layer 4 and the external electrode 5 extending to the upper surface of the substrate 1 may be in contact with the sidewall of the stacked structure formed by the resistive layer 6 , the first protective layer 7 and the second protective layer 8 . get in touch with.
  • the present application also provides a method for preparing a patch electrode, including:
  • S23 forming an upper electrode, a barrier layer and an external electrode; wherein, one end of the upper electrode is in contact with the bottom electrode, and the other end extends to the upper surface of the substrate through the sidewall of the substrate; the barrier layer is located on the surface of the upper electrode away from the substrate; the external electrode is located at The barrier layer is away from the surface of the upper electrode;
  • S25 Prepare lead-free glass paste by using the preparation method for lead-free glass paste as described in any one of the above embodiments;
  • the lead-free glass paste prepared by the preparation method of the lead-free glass paste in any of the above-mentioned embodiments is used to prepare the first protective layer, which not only meets the environmental protection requirements, but also has better performance.
  • Thermal stability, temperature resistance temperature can reach above 640 °C.
  • the substrate 1 provided in step S21 may include, but is not limited to, an alumina substrate.
  • the bottom electrode 2 may be formed by, but not limited to, a deposition process or an electroplating process, and the bottom electrode 2 may include, but is not limited to, a silver electrode.
  • step S23 may include the following steps:
  • the upper electrode material layer may be formed by, but not limited to, a deposition process or an electroplating process;
  • S232 forming a barrier material layer on the surface of the upper electrode material layer, specifically, but not limited to a deposition process or an electroplating process to form the barrier material layer;
  • S233 forming an external electrode material layer on the surface of the barrier material layer; specifically, the external electrode material layer may be formed by but not limited to a deposition process or an electroplating process;
  • S234 Etch the upper electrode material layer, the barrier material layer and the outer electrode material layer to form the upper electrode, the barrier layer and the outer electrode.
  • the upper electrode 3 may include, but not limited to, a silver electrode, a palladium electrode, or a mixed electrode of silver and palladium;
  • the barrier layer 4 may include, but is not limited to, a nickel layer; and
  • the external electrode 5 may include, but is not limited to, a tin electrode.
  • the resistance layer 6 may be formed by but not limited to a deposition process, and one end of the resistance layer 6 may be in contact with the upper electrode, the barrier layer and the end of the external electrode extending to the upper surface of the substrate 1 .
  • the resistance layer 6 may include, but is not limited to, a ruthenium oxide layer.
  • the second protective layer 8 may be formed by, but not limited to, a spin coating process; the second protective layer 8 may include, but is not limited to, an epoxy resin layer.

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Abstract

提供一种无铅玻璃浆料、贴片电阻及其制备方法。该无铅玻璃浆料，按质量份计，包括如下组分：硼硅油6～7份，氧化铝粉末12～21份，玻璃纤维粉2～3份及固化剂0.1～0.5份。

Description

无铅玻璃浆料、贴片电阻及其制备方法
相关申请的交叉引用
本申请要求于2020年7月22日提交中国专利局、申请号为202010710018.6、申请名称为“无铅玻璃浆料、贴片电阻及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于封装材料技术领域，具体涉及一种无铅玻璃浆料、贴片电阻及其制备方法。
技术背景
现有的贴片电阻中一般使用玻璃浆料制备保护层，而现有的玻璃浆料中会含有大量的氧化铅，虽然采用该玻璃浆料制备的贴片电阻的铅含量属于法规豁免范围，但含铅的玻璃浆料中的铅会造成环境污染，故行业、客户及法规都在致力于贴片电阻的无铅化。
现有技术中一般通过替换氧化铅来降低玻璃浆料中的含铅量或实现玻璃浆料无铅化，然而现有的无铅玻璃浆料均存在耐高温能力较差的问题，而贴片电阻在工作时会产生大量的热量，现有的无铅玻璃浆料无法满足贴片电阻的需求。
发明内容
根据本申请的各种实施例，提供一种无铅玻璃浆料、贴片电阻及其制备方法。
本申请提供一种无铅玻璃浆料，按质量份计，包括如下组分：硼硅油6～7份，氧化铝粉末12～21份，玻璃纤维粉2～3份及固化剂0.1～0.5份。
上述实施例中的无铅玻璃浆料为无铅玻璃浆料，既符合环保要求，又具 有较好的热稳定性，耐热温度可以达到640℃以上。
在其中一个实施例中，按质量份计，所述硼硅油包括如下组分：含苯基硅物质100～115份、含硼单体13～28份、硅烷50～75份及二羟基吡啶60～80份。
在其中一个示例中，所述含苯基硅物质包括：乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的至少一种；所述硅烷包括：二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的至少一种；所述二羟基吡啶包括：2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的至少一种；所述含硼单体包括硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的至少一种。
在其中一个实施例中，氧化铝粉末包括纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的至少一种。
在其中一个实施例中，玻璃纤维粉包括无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的至少一种。
在其中一个实施例中，所述固化剂包括TMO、双25、二月桂酸二丁基锡、二乙酸二丁基锡及DCP中的至少一种。
在其中一个实施例中，无铅玻璃浆料的化学结构式为：
Figure PCTCN2021098826-appb-000001
其中，x:y＝1.1～1.9：0.3～0.7；R 1为苯基、羟基或乙醇基；R 2为甲基、乙基或苯基；R 3为二羟基吡啶。
本申请的还提供一种如上述任意实施例中所述的无铅玻璃浆料的制备方法，包括：
制备硼硅油；
将所述硼硅油与氧化铝粉末及玻璃纤维粉混合均匀以得到混合物；及
于所述混合物中加入固化剂进行固化后破碎，以得到所述无铅玻璃浆料。
上述实施例中制备的无铅玻璃浆料为无铅玻璃浆料，既符合环保要求，又具有较好的热稳定性，耐热温度可以达到640℃以上。
在其中一个实施例中，制备硼硅油包括：
称取含苯基硅物质及含硼单体，将称取的所述含苯基硅物质及所述含硼单体加入第一溶剂中搅拌均匀反应后去除所述第一溶剂，以得到第一产物；
称取硅烷及二羟基吡啶，将称取的所述硅烷及所述二羟基吡啶加入第二溶剂中搅拌均匀反应后去除所述第二溶剂，以得到第二产物；及
称取第一产物及第二产物，将称取的所述第一产物及所述第二产物加入第三溶剂中，搅拌均匀反应后得到所述硼硅油。
在其中一个实施例中，，称取的所述含苯基硅物质的质量为100g～115g，称取的所述含硼单体的质量为13g～28g，所述第一溶剂的体积为150ml～250ml，所述第一溶剂包括二氯乙烷溶剂；称取的所述硅烷的质量为50g～75g，称取的所述二羟基吡啶的质量为60g～80g，所述第二溶剂的体积为350ml～450ml，所述第二溶剂包括乙酸丙酯溶剂；称取的所述第一产物的质量份为1份～1.1份，称取的所述第二产物的质量份为0.95份～1份，所述第三溶剂的体积为95ml～150ml，所述第三溶剂包括丙酮。
在其中一个实施例中，得到所述第一产物的过程中的反应温度为50℃～75℃，反应时间为2.5h～3.5h；得到所述第二产物的过程中的反应温度为60℃～90℃，反应时间为1.5h～2.5h；得到所述硼硅油的过程中的反应温度为35℃～45℃，反应时间为5.5h～6.5h。
在其中一个实施例中，所述固化反应的温度为26℃～45℃，固化反应的时间为5h～7h。
本申请的还提供一种贴片电阻，包括：
基板；
底部电极，位于所述基板的下表面；
上部电极，一端与所述底部电极相接触，另一端自所述基板的侧壁延伸至所述基板的上表面；
阻隔层，位于所述上部电极远离所述基板的表面；
外部电极，位于所述阻隔层远离所述上部电极的表面；
电阻层，位于所述基板的上表面，且位于所述上部电极的一侧；
第一保护层，位于所述电阻层的上表面；所述第一保护层由如上市任意实施例中所述的无铅玻璃浆料制备而成；及
第二保护层，位于所述第一保护层的上表面。
上述实施例中的贴片电阻中采用上述任意实施例中的无铅玻璃浆料制备第一保护层，既符合环保要求，又具有较好的热稳定性，耐温温度可以达到640℃以上。
本申请的还提供一种贴片电阻的制备方法，包括：
提供基板；
于所述基板的下表面形成底部电极；
形成上部电极、阻隔层及外部电极；其中，所述上部电极一端与所述底部电极相接触，另一端经由所述基板的侧壁延伸至所述基板的上表面；所述阻隔层位于所述上部电极远离所述基板的表面；所述外部电极位于所述阻隔层远离所述上部电极的表面；
于所述基板的上表面形成电阻层，所述电阻层位于所述上部电极的一侧；
采用如上述任一实施例中所述的无铅玻璃浆料的制备方法制备无铅玻璃浆料；
将所述无铅玻璃浆料涂覆于所述电阻层的上表面以形成第一保护层；及
于所述第一保护层的上表面形成第二保护层。
上述实施例中的贴片电阻的制备方法中采用上述任意实施例中的无铅玻璃浆料的制备方法制备的无铅玻璃浆料制备第一保护层，既符合环保要求，又具有较好的热稳定性，耐温温度可以达到640℃以上。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他实施例的附图。
图1为本申请一实施例中提供的无铅玻璃浆料的制备方法的流程图。
图2为本申请一实施例中提供的无铅玻璃浆料的制备方法中制备硼硅油的流程图。
图3为本申请另一个实施例中提供的贴片电阻的截面结构示意图。
图4为本申请又一个实施例中提供的贴片电阻的制备方法的流程图。
附图标记说明：1、基板；2、底部电极；3、上部电极；4、隔离层；5、外部电极；6、电阻层；7、第一保护层；8、第二保护层。
具体实施方式
为了便于理解本申请，下面将参照相关附图对本申请进行更全面的描述。附图中给出了本申请的实施例。但是，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本申请的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
在使用本文中描述的“包括”、“具有”、和“包含”的情况下，除非使用了明确的限定用语，例如“仅”、“由……组成”等，否则还可以添加另一部件。除非相反地提及，否则单数形式的术语可以包括复数形式，并不能理解为其数量为一个。
本申请提供一种无铅玻璃浆料，按质量份计，包括如下组分：硼硅油6～7份，氧化铝粉末12～21份，玻璃纤维粉2～3份及固化剂0.1～0.5份。
上述实施例中的无铅玻璃浆料为无铅玻璃浆料，符合环保要求，且该无铅玻璃浆料具有较好的热稳定性，耐热温度可以达到640℃以上。
在一个示例中，无铅玻璃浆料按质量份计，可以包括如下组分：硼硅油6.2～6.8份，具体的，硼硅油可以为6.2份、6.5份或6.8份；氧化铝粉末15～18份，具体的，氧化硅粉末可以为15份、16份、17份或18份；玻璃纤维粉2.2～2.8份，具体的，玻璃纤维粉可以为2.2份、2.5份或2.8份；及固化剂0.2～0.4份，具体的，固化剂可以为0.2份、0.3份或0.4份。
在其中一个示例中，按质量份计，硼硅油可以包括如下组分：含苯基硅物质100～115份、含硼单体13～28份、硅烷50～75份及二羟基吡啶60～80份；具体的，硼硅油中，含硅物质可以为100份、105份、110份或115份，含硼单体可以为13份、15份、20份、25份或28份，硅烷可以为50份、55份、60份、65份、70份或75份，二羟基吡啶可以为60份、65份、70份、75份或80份。
在其中一个示例中，含苯基硅物质包括：乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的至少一种，即含苯基硅物质可以包括乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的任意一种，也可以为乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的任意两种或两种以上的组合。
在一个示例中，硅烷包括：二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的至少一种，即硅烷可以为二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的任意一种，也可以为二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的任意两种或两种以上的组合。
在一个示例中，二羟基吡啶包括：2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的至少一种，即二羟基吡啶可以为2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的任意一种，也可以为2,4-二羟基吡啶、2,6-二羟基 吡啶及3,5-二羟基吡啶中的任意两种或两种以上的组合。
在一个示例中，含硼单体包括硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的至少一种，即含硼单体可以为硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的任意一种，也可以为硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的任意两种或两种以上的组合。
在其中一个示例中，氧化铝粉末包括纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的至少一种；即氧化铝粉末可以为纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的任意一种，也可以为纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的中的任意两种或两种以上的组合。
在其中一个示例中，玻璃纤维粉包括无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的至少一种；即玻璃纤维粉可以为无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的任意一种，也可以为无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的任意两种或两种以上的组合。
在其中一个示例中，固化剂包括TMO(四甲氧基硅烷)、双25(2,5-二甲基-2,5-双(过氧化叔丁基)己烷)、二月桂酸二丁基锡、二乙酸二丁基锡及DCP(过氧化二异丙苯)中的至少一种；即固化剂可以为TMO、双25、二月桂酸二丁基锡、二乙酸二丁基锡及DCP中的任意一种，也可以为TMO、双25、二月桂酸二丁基锡、二乙酸二丁基锡及DCP中的任意两种或两种以上的组合。
在其中一个示例中，无铅玻璃浆料的化学结构式可以为：
Figure PCTCN2021098826-appb-000002
其中，x:y＝1.1～1.9：0.3～0.7；R 1为苯基、羟基或乙醇基；R 2为甲基、乙基或苯基；R 3为二羟基吡啶。
在另一个实施例中，请参阅图1，本申请还提供一种如上述任意方案中所述的无铅玻璃浆料的制备方法，包括：
S11：制备硼硅油；
S12：将硼硅油与氧化铝粉末及玻璃纤维粉混合均匀以得到混合物；及
S13：于混合物中加入固化剂进行固化后破碎，以得到所述无铅玻璃浆料。
在一个示例中，如图2所示，步骤S11可以包括如下步骤：
S111：称取含苯基硅物质及含硼单体，将称取的含硅物质及含硼单体加入第一溶剂中搅拌均匀反应后去除第一溶剂，以得到第一产物；
S112：称取硅烷及二羟基吡啶，将称取的硅烷及二羟基吡啶加入第二溶剂中搅拌均匀反应后去除所述第二溶剂，以得到第二产物；及
S113：称取第一产物及第二产物，将称取的第一产物及第二产物加入第三溶剂中，搅拌均匀反应后得到硼硅油。
具体的，步骤S111中，称取的含苯基硅物质的质量可以为100g～115g，譬如，可以为100g、105g、110g或115g等等；称取的含硼单体的质量可以为13g～28g，譬如，13g、15g、20g、25g或28g等等；第一溶剂可以包括二氯乙烷溶剂，第一溶剂的体积可以为150ml～200ml，譬如，150ml、160ml、170ml、180ml、190ml或200ml。
在一个示例中，步骤S112中，称取的硅烷的质量可以为50g～75g，譬如，可以为50g、55g、60g、65g、70g或75g等等；称取的二羟基吡啶的质量可以为60g～80g，譬如，可以为60g、65g、70g、75g、80g等等；第二溶剂可以包括乙酸丙酯溶剂，第二溶剂的体积可以为350ml～450ml，，譬如，可以为350ml、400ml或450ml等等。
在一个示例中，步骤S113中，称取的第一产物的质量份可以为1份～1.1份，譬如，可以为1份、1.01份、1.05份或1.1份等等；称取的第二产物的质量份可以为0.95份～1份，譬如，可以为0.95份或1份等等；第三溶剂可 以包括丙酮，第三溶剂的体积可以为95ml～150ml，譬如，可以为95ml、100ml、110ml、120ml、130ml、140ml或150ml等等。
在一个示例中，步骤S111中，反应后在低压(低于常压)条件下去除第一溶剂；步骤S111中的反应温度可以为50℃～75℃，反应时间可以为2.5h～3.5h；具体的，该步骤中的反应温度可以为50℃、60℃、70℃或75℃等等；反应时间可以为2.5h、3h或3.5h等等。
在一个示例中，步骤S112中，在低压条件下去除第二溶剂；步骤S112中的反应温度可以为60℃～90℃，反应时间可以为1.5h～2.5h；具体的，该步骤的反应温度可以为60℃、70℃、80℃或90℃等等，反应时间可以为1.5h、2h或2.5h等等。
在一个示例中，步骤S113中，反应温度可以为35℃～45℃，反应时间可以为5.5h～6.5h；具体的，反应温度可以为35℃、40℃或45℃等等，反应时间可以为5.5h、6h或6.5h等等。
在其中一个示例中，含苯基硅物质包括：乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的至少一种，即含苯基硅物质可以包括乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的任意一种，也可以为乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的任意两种或两种以上的组合。
在一个示例中，硅烷包括：二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的至少一种，即硅烷可以为二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的任意一种，也可以为二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的任意两种或两种以上的组合。
在一个示例中，二羟基吡啶包括：2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的至少一种，即二羟基吡啶可以为2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的任意一种，也可以为2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的任意两种或两种以上的组合。
在一个示例中，含硼单体包括硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼 烷的至少一种，即含硼单体可以为硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的任意一种，也可以为硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的任意两种或两种以上的组合。
在一个示例中，步骤S12中，按质量份计，称取6～7份步骤S1制备得到的硼硅油，称取12～21份的氧化铝粉末，并称取2～3份的玻璃纤维粉，将称取的硼硅油、氧化铝粉末即玻璃纤维粉混合均匀；具体的，称取的硼硅油的质量份可以为6份、6.5份或7份，称取的氧化铝粉末的质量份可以为12份、15份或21份等等，称取的剥离纤维粉的质量份可以为2份、2.5份或3份等等。
在其中一个示例中，氧化铝粉末包括纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的至少一种；即氧化铝粉末可以为纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的任意一种，也可以为纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的中的任意两种或两种以上的组合。
在其中一个示例中，玻璃纤维粉包括无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的至少一种；即玻璃纤维粉可以为无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的任意一种，也可以为无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的任意两种或两种以上的组合。
在一个示例中，步骤S13中，将步骤S2得到的混合物中加入固化剂，加入的固化剂的质量份可以为0.1份～0.5份，搅拌均匀，低压脱除气泡，并于预设温度下固化反应一定时间得到反应产物；具体的，加入的固化剂的质量份可以为0.1份、0.2份、0.3份、0.4份或0.5份。
具体的，固化反应的温度可以为26℃～45℃，譬如，26℃、30℃、35℃、40℃、或45℃等等；固化反应的时间可以为5h～7h，譬如，5h、6h或7h。
在一个示例中，步骤S13中可以采用任意一种破碎工艺将得到的反应产物进行破碎以得到无铅玻璃浆料。
在其中一个示例中，固化剂包括TMO、双25、二月桂酸二丁基锡、二乙酸二丁基锡及DCP中的至少一种；即固化剂可以为TMO、双25、二月桂酸二丁基锡、二乙酸二丁基锡及DCP中的任意一种，也可以为TMO、双25、二月桂酸二丁基锡、二乙酸二丁基锡及DCP中的任意两种或两种以上的组合。
上述实施例中制备得到的无铅玻璃浆料为无铅玻璃浆料，符合环保要求，且该无铅玻璃浆料具有较好的热稳定性，耐热温度可以达到640℃以上。
下面以具体实施例来对本申请中的无铅玻璃浆料的制备方法进一步的进行描述说明。
实施例1
步骤1：在烧杯中加入二氯苯硼烷26g，溶于200mL的二氯乙烷，溶解后加入500mL的四口烧瓶中，再加入100g二乙氧基二苯基硅烷，通氮气，在氮气气氛下升温至55℃，机械搅拌，转速为500r/min，搅拌反应3h后减压至真空泵表压为-0.05MPa去除溶剂，得到第一产物A；称取70g二氯二甲基硅烷，溶于400mL的乙酸丙酯，溶解后加入1000mL的四口烧瓶中，再加入75g的2，6二羟基吡啶，通氮气，在氮气气氛下升温至66℃，机械搅拌，转速为500r/min，搅拌反应2h后减压至真空泵表压为-0.05MPa去除溶剂，得到第二产物B；取1.01份的第一产物A，1份的第二产物B，溶于100mL的丙酮中，溶解后加入250mL的四口烧瓶中，40℃下反应6h，得到特殊的硼硅油；
步骤2：称取6.2份的硼硅油，加入16份的α型纳米氧化铝粉末，加入无碱玻璃纤维粉，混合得到混合物；
步骤3：于混合物中加入固化剂双25，搅拌均匀，低压脱除气泡，35℃下反应6h得到产物，利用破碎机破碎产物得到玻璃浆。本实施例1中所制备的玻璃浆耐热达到689℃。
在又一个实施例中，请参阅图3，本申请还提供一种贴片电阻，包括：基板1；底部电极2，底部电极2位于基板1的下表面；上部电极3，上部电极3一端与底部电极2相接触，另一端自基板1的侧壁延伸至基板1的上表面；阻隔层4，阻隔层4位于上部电极3远离基板1的表面；外部电极5，外 部电极5位于阻隔层4远离上部电极3的表面；电阻层6，电阻层6位于基板1的上表面，且电阻层6位于上部电极3的一侧；第一保护层7，第一保护层7位于电阻层6的上表面；第一保护层7可以由如上述任一实施例中的无铅玻璃浆料制备而成，无铅玻璃浆料的具体组分及特征请参阅上述实施例，此处不再累述；第二保护层8，第二保护层8位于第一保护层7的上表面。
上述实施例中的贴片电阻中采用上述任意实施例中的无铅玻璃浆料制备第一保护层7，既符合环保要求，又具有较好的热稳定性，耐温温度可以达到640℃以上。
在一个示例中，基板1可以包括但不仅限于氧化铝基板；底部电极2可以包括但不仅限于银电极；上部电极3可以包括但不仅限于银电极、钯电极或银及钯混合电极；阻隔层4可以包括但不仅限于镍层；外部电极5可以包括但不仅限于锡电极；电阻层6可以包括但不仅限于氧化钌层；第二保护层8可以包括但不仅限于环氧树脂层。
在一个示例中，上部电极3、隔离层4及外部电极5延伸至基板1上表面的一段可以与电阻层6、第一保护层7及第二保护层8形成的叠层结构的侧壁相接触。
在又一实施例中，请结合图3参阅图4，本申请还提供一种贴片电极的制备方法，包括：
S21：提供基板；
S22：于基板的下表面形成底部电极；
S23：形成上部电极、阻隔层及外部电极；其中，上部电极一端与底部电极相接触，另一端经由基板的侧壁延伸至基板的上表面；阻隔层位于上部电极远离基板的表面；外部电极位于阻隔层远离上部电极的表面；
S24：于基板的上表面形成电阻层，电阻层位于上部电极的一侧；
S25：采用如上述任一实施例中所述的无铅玻璃浆料的制备方法制备无铅玻璃浆料；
S26：将无铅玻璃浆料涂覆于电阻层的上表面以形成第一保护层；
S27：于第一保护层的上表面形成第二保护层。
上述实施例中的贴片电阻的制备方法中采用上述任意实施例中的无铅玻璃浆料的制备方法制备的无铅玻璃浆料制备第一保护层，既符合环保要求，又具有较好的热稳定性，耐温温度可以达到640℃以上。
在一个示例中，步骤S21中提供的基板1可以包括但不仅限于氧化铝基板。
在一个示例中，步骤S22中，可以采用但不仅限于沉积工艺或电镀工艺形成底部电极2，底部电极2可以包括但不仅限于银电极.
在一个示例中，步骤S23可以包括如下步骤：
S231：于所述基板1的上表面、侧壁及底部电极2的表面形成上部电极材料层；具体的，可以采用但不仅限于沉积工艺或电镀工艺形成上部电极材料层；
S232：于所述上部电极材料层的表面形成阻隔材料层，具体的，可以采用但不仅限于沉积工艺或电镀工艺形成阻隔材料层；
S233：于所述阻隔材料层的表面形成外部电极材料层；具体的，可以采用但不仅限于沉积工艺或电镀工艺形成外部电极材料层；
S234：对上部电极材料层、阻隔材料层及外部电极材料层进行刻蚀以形成上部电极、阻隔层及外部电极。
在一个示例中，上部电极3可以包括但不仅限于银电极、钯电极或银及钯混合电极；阻隔层4可以包括但不仅限于镍层；外部电极5可以包括但不仅限于锡电极。
在一个示例中，步骤S24中，可以采用但不仅限于沉积工艺形成电阻层6，电阻层6的一端可以与上部电极、阻隔层及外部电极延伸至基板1上表面的一端相接触。电阻层6可以包括但不仅限于氧化钌层。
在一个示例中，可以采用但不仅限于旋涂工艺形成第二保护层8；第二保护层8可以包括但不仅限于环氧树脂层。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未 对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (14)

  1. 一种无铅玻璃浆料，按质量份计，包括如下组分：硼硅油6～7份，氧化铝粉末12～21份，玻璃纤维粉2～3份及固化剂0.1～0.5份。
  2. 根据权利要求1所述的无铅玻璃浆料，其中，按质量份计，所述硼硅油包括如下组分：含苯基硅物质100～115份、含硼单体13～28份、硅烷50～75份及二羟基吡啶60～80份。
  3. 根据权利要求2所述的无铅玻璃浆料，其中，所述含苯基硅物质包括：乙氧基二苯基硅烷、二苯基二甲氧基硅烷及二苯基硅二醇中的至少一种；所述硅烷包括：二氯二甲基硅烷、二氯二乙基硅烷及二氯二苯基硅烷的至少一种；所述二羟基吡啶包括：2,4-二羟基吡啶、2,6-二羟基吡啶及3,5-二羟基吡啶中的至少一种；所述含硼单体包括硼酸、苯硼酸、硼酸三异丙酯及二氯苯硼烷的至少一种。
  4. 根据权利要求1所述的无铅玻璃浆料，其中，所述氧化铝粉末包括纳米级氧化铝粉末、气相氧化铝粉末及α型纳米级氧化铝粉末中的至少一种。
  5. 根据权利要求1所述的无铅玻璃浆料，其中，所述玻璃纤维粉包括无碱玻璃纤维粉、耐碱玻璃纤维粉、高碱玻璃纤维粉及中碱玻璃纤维粉中的至少一种。
  6. 根据权利要求1所述的无铅玻璃浆料，其中，所述固化剂包括四甲氧基硅烷(TMO)、2,5-二甲基-2,5-双(过氧化叔丁基)己烷(双25)、二月桂酸二丁基锡、二乙酸二丁基锡及过氧化二异丙苯(DCP)中的至少一种。
  7. 根据权利要求1所述的无铅玻璃浆料，其中，所述无铅玻璃浆料的化学结构式为：
    Figure PCTCN2021098826-appb-100001
    其中，x:y＝1.1～1.9：0.3～0.7；R 1为苯基、羟基或乙醇基；R 2为甲基、乙基或苯基；R 3为二羟基吡啶。
  8. 一种如权利要求1至7中任一项所述的无铅玻璃浆料的制备方法，包括：
    制备硼硅油；
    将所述硼硅油与氧化铝粉末及玻璃纤维粉混合均匀以得到混合物；及
    于所述混合物中加入固化剂进行固化反应后破碎，以得到所述无铅玻璃浆料。
  9. 根据权利要求8所述的无铅玻璃浆料的制备方法，其中，制备硼硅油包括：
    称取含苯基硅物质及含硼单体，将称取的所述含苯基硅物质及所述含硼单体加入第一溶剂中搅拌均匀反应后去除所述第一溶剂，以得到第一产物；
    称取硅烷及二羟基吡啶，将称取的所述硅烷及所述二羟基吡啶加入第二溶剂中搅拌均匀反应后去除所述第二溶剂，以得到第二产物；及
    称取第一产物及第二产物，将称取的所述第一产物及所述第二产物加入第三溶剂中，搅拌均匀反应后得到所述硼硅油。
  10. 根据权利要求9所述的无铅玻璃浆料的制备方法，其中，称取的所述含苯基硅物质的质量为100g～115g，称取的所述含硼单体的质量为13g～28g，所述第一溶剂的体积为150ml～250ml，所述第一溶剂包括二氯乙烷溶剂；称取的所述硅烷的质量为50g～75g，称取的所述二羟基吡啶的质量为60g～80g，所述第二溶剂的体积为350ml～450ml，所述第二溶剂包括乙酸丙酯溶剂；称取的所述第一产物的质量份为1份～1.1份，称取的所述第二产物的质量份为0.95份～1份，所述第三溶剂的体积为95ml～150ml，所述第三溶剂包括丙酮。
  11. 根据权利要求9所述的无铅玻璃浆料的制备方法，其中，得到所述第一产物的过程中的反应温度为50℃～75℃，反应时间为2.5h～3.5h；得到所述第二产物的过程中的反应温度为60℃～90℃，反应时间为1.5h～2.5h；得到 所述硼硅油的过程中的反应温度为35℃～45℃，反应时间为5.5h～6.5h。
  12. 根据权利要求8所述的无铅玻璃浆料的制备方法，其中，所述固化反应的温度为26℃～45℃，固化反应的时间为5h～7h。
  13. 一种贴片电阻，包括：
    基板；
    底部电极，位于所述基板的下表面；
    上部电极，一端与所述底部电极相接触，另一端自所述基板的侧壁延伸至所述基板的上表面；
    阻隔层，位于所述上部电极远离所述基板的表面；
    外部电极，位于所述阻隔层远离所述上部电极的表面；
    电阻层，位于所述基板的上表面，且位于所述上部电极的一侧；
    第一保护层，位于所述电阻层的上表面；所述第一保护层由如权利要求1至7中任一项所述的无铅玻璃浆料制备而成；及
    第二保护层，位于所述第一保护层的上表面。
  14. 一种贴片电阻的制备方法，包括：
    提供基板；
    于所述基板的下表面形成底部电极；
    形成上部电极、阻隔层及外部电极；其中，所述上部电极一端与所述底部电极相接触，另一端经由所述基板的侧壁延伸至所述基板的上表面；所述阻隔层位于所述上部电极远离所述基板的表面；所述外部电极位于所述阻隔层远离所述上部电极的表面；
    于所述基板的上表面形成电阻层，所述电阻层位于所述上部电极的一侧；
    采用如权利要求8至12中任一项所述的无铅玻璃浆料的制备方法制备无铅玻璃浆料；
    将所述无铅玻璃浆料涂覆于所述电阻层的上表面以形成第一保护层；及
    于所述第一保护层的上表面形成第二保护层。
PCT/CN2021/098826 2020-07-22 2021-06-08 无铅玻璃浆料、贴片电阻及其制备方法 Ceased WO2022017023A1 (zh)

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