CN116206800B - Medium slurry and preparation method thereof - Google Patents
Medium slurry and preparation method thereof Download PDFInfo
- Publication number
- CN116206800B CN116206800B CN202310475902.XA CN202310475902A CN116206800B CN 116206800 B CN116206800 B CN 116206800B CN 202310475902 A CN202310475902 A CN 202310475902A CN 116206800 B CN116206800 B CN 116206800B
- Authority
- CN
- China
- Prior art keywords
- photo
- barium titanate
- photosensitive resin
- agent
- organic carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/447—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from acrylic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
- H01B3/085—Particles bound with glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a medium slurry and a preparation method thereof, which belong to the technical field of electronic materials, wherein the medium slurry comprises the following components in percentage by mass: 10-20% of organic carrier, 60-80% of glass powder and 1-10% of modifying additive; the organic carrier comprises the following components in percentage by mass: 50-70% of photosensitive resin, 3-5% of photo-curing prepolymer, 3-5% of photo-curing monomer, 3-5% of photoinitiator, 15-25% of solvent, 0.3-2% of flatting agent, 0.3-2% of defoaming agent and 0.3-2% of dispersing agent; the molecular structure of the photosensitive resin contains photosensitive groups and alkali-soluble groups. The invention prepares the dielectric paste with excellent performance by taking the organic carrier, the glass powder and the modified additive as raw materials, and the dielectric paste has excellent dielectric constant, insulating performance and stability and can stably exist in an acidic system.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a dielectric paste and a preparation method thereof.
Background
The existing high-temperature dielectric materials mainly comprise thick film glass paste, ceramic plates, glass plates, LTCC/HTCC ceramic green belts and the like. These materials generally do not achieve pattern dimensional accuracy below 1 mm. LTCC and HTCC can achieve openings above 100 μm by mechanical punching, but cannot achieve more precise circular openings, nor can it achieve shaped patterns or shaped openings. The ceramic sheet and the glass sheet can be inserted into the circuit in a bonding mode, but the insulating property is poor, and the chemical stability is required to be improved.
CN114049986a discloses a high-performance lead-bismuth-free medium slurry, which consists of, by weight, 100% of modified glass powder 60% -85% and organic carriers 15% -40%; the modified glass powder is obtained by mixing Ba-Si-Zn-Al-Pt glass powder with methallyl alcohol and then carrying out vibration grinding modification treatment; the organic carrier consists of ethyl cellulose, lecithin and methallyl alcohol; the particle size of the powder particles can be more concentrated through the vibration grinding treatment of the glass powder, but the vibration grinding energy is larger, so that the appearance of the glass powder is easily damaged on a large scale, and the situation can be effectively avoided by adding methallyl alcohol as a coating agent; and the heating condition is serious in the use process of the vibration mill, and the methallyl alcohol has good thermal stability; but its insulation properties remain to be improved.
Therefore, how to improve the chemical stability and the insulation performance of the dielectric paste is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a dielectric paste and a preparation method thereof, wherein the dielectric paste has excellent insulating property and stability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the medium slurry comprises the following components in percentage by mass: 10-20% of organic carrier, 60-80% of glass powder and 1-10% of modifying additive;
the organic carrier comprises the following components in percentage by mass: 50-70% of photosensitive resin, 3-5% of photo-curing prepolymer, 3-5% of photo-curing monomer, 3-5% of photoinitiator, 15-25% of solvent, 0.3-2% of flatting agent, 0.3-2% of defoaming agent and 0.3-2% of dispersing agent;
the molecular structure of the photosensitive resin contains photosensitive groups and alkali-soluble groups;
the photo-curing prepolymer is at least one of unsaturated compound containing epoxy group and unsaturated compound containing ethoxy group;
the photo-curing monomer comprises at least one of methyl methacrylate, hexafluorobutyl methacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxylated trimethylolpropane triacrylate and trimethylolpropane triacrylate.
In a preferred embodiment of the present invention, the photosensitive resin has an acid value of 70 to 100mgKOH/g, and the photosensitive resin is an aqueous alkali-soluble acrylic resin.
As a preferred embodiment of the present invention, the epoxy group-containing unsaturated compound includes at least one of glycidyl acrylate, glycidyl methacrylate, α -n-propyl glycidyl acrylate, β -ethyl glycidyl methacrylate; and/or
The unsaturated compound containing ethoxy comprises at least one of ethoxylated trimethylolpropane triacrylate and polyethylene glycol diacrylate.
As a preferred embodiment of the present invention, the photoinitiator is at least one of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 4-isopropylthioxanthone, 1-hydroxycyclohexylphenyl methanone, bis 2, 6-difluoro-3-pyrrolophenyltitanocene, triphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide; and/or
The solvent comprises at least one of dimethyl oxalate, diethyl oxalate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dipropyl adipate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, terpineol, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate.
As a preferred embodiment of the present invention, the dispersant includes at least one of polyester-based dispersants, polyether-based dispersants; and/or
The leveling agent comprises at least one of acrylic polysiloxane, polyether modified polysiloxane, polysiloxane polyether copolymer and polysiloxane; and/or
The defoamer comprises at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate and organic silicon resin.
As a preferred embodiment of the present invention, the preparation method of the modifying additive comprises the steps of:
(1) Uniformly mixing barium titanate and aluminum ammonium sulfate, calcining for 2-8 hours at 1100-1200 ℃, and ball milling to obtain barium titanate coated with aluminum oxide;
(2) Adding cashew nut shell oil dihydric alcohol, an isocyanate silane coupling agent and a catalyst into a reaction kettle, reacting for 4-12 hours at 55-70 ℃ under the protection of nitrogen, and filtering to obtain a modifier;
(3) Adding the modifier into an organic solvent, dispersing uniformly, adding barium titanate wrapped by alumina, performing ultrasonic treatment at 55-65 ℃ for 2-6 hours, filtering, and drying to obtain the modified additive.
As a preferred embodiment of the present invention, the mass ratio of the barium titanate to the aluminum ammonium sulfate is 1: (0.2 to 0.6); and/or
The mass ratio of the cashew nut shell oil dihydric alcohol to the isocyanate silane coupling agent to the catalyst is (1-4): 1: (0.02-0.08).
As a preferred embodiment of the present invention, the mass ratio of the modifier, the solvent, and the alumina-coated barium titanate is 1: (5-20): (2-10).
As a preferred embodiment of the present invention, the isocyanatosilane coupling agent includes at least one of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl methyl dimethoxysilane;
the catalyst comprises an organobismuth catalyst;
the organic solvent comprises at least one of methanol, ethanol and acetone.
The invention also provides a preparation method of the medium slurry, which comprises the following steps:
uniformly mixing photosensitive resin, photo-curing prepolymer, photo-curing monomer, photo-initiator, solvent, leveling agent, defoaming agent and dispersing agent to obtain an organic carrier;
mixing the organic carrier, the glass powder and the modifying additive uniformly, grinding and filtering to obtain the medium slurry.
The invention has the beneficial effects that: (1) The invention prepares the medium slurry with excellent performance by taking the organic carrier, the glass powder and the modified additive as raw materials, and the medium slurry has excellent insulating performance and stability and can stably exist in an acidic system; (2) By selecting the photosensitive resin with the photosensitive group and the alkali-soluble group in the molecular structure, the affinity with the glass powder and the modified additive can be effectively improved, the glass powder and the modified additive can be well wetted, the dispersibility of the system is improved, and the chemical stability and the insulating property of the slurry are further improved.
Drawings
FIG. 1 is a flow chart of a test case.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
In the present invention, the specific dispersing and stirring treatment method is not particularly limited.
The reagents or apparatus used in the present invention are conventional products commercially available without the manufacturer's knowledge.
The embodiment of the invention provides a medium slurry, which comprises the following components in percentage by mass: 10-20% of organic carrier, 60-80% of glass powder and 1-10% of modifying additive;
the organic carrier comprises the following components in percentage by mass: 50-70% of photosensitive resin, 3-5% of photo-curing prepolymer, 3-5% of photo-curing monomer, 3-5% of photoinitiator, 15-25% of solvent, 0.3-2% of flatting agent, 0.3-2% of defoaming agent and 0.3-2% of dispersing agent;
the molecular structure of the photosensitive resin contains photosensitive groups and alkali-soluble groups;
the photo-curing prepolymer is at least one of unsaturated compound containing epoxy group and unsaturated compound containing ethoxy group;
the photo-curing monomer comprises at least one of methyl methacrylate, hexafluorobutyl methacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxylated trimethylolpropane triacrylate and trimethylolpropane triacrylate.
The invention prepares the dielectric paste with excellent performance by taking the organic carrier, the glass powder and the modified additive as raw materials, and the dielectric paste has excellent dielectric constant, insulating performance and stability and can stably exist in an acidic system.
The photosensitive resin with the molecular structure containing the photosensitive group and the alkali-soluble group is selected, so that the affinity with the glass powder and the modified additive can be effectively improved, the glass powder and the modified additive can be well wetted, the dispersibility of a system is improved, and the chemical stability and the insulating property of the slurry are further improved.
Wherein, by selecting unsaturated compound containing epoxy group and adopting the photo-curing monomer of the invention, stable chemical bond can be formed, and the performance is stable.
In one embodiment, the photosensitive resin has an acid value of 70-100 mgKOH/g, and the photosensitive resin is an aqueous alkali-soluble acrylic resin. Particularly, the aqueous alkali-soluble acrylic resin with the acid value of 70-100 mgKOH/g is selected as the photosensitive resin, so that the chemical stability, the electric conductivity and the adhesive force can be improved more effectively.
Exemplary are Neocryl BT-24, neocryl BT-21, the product types of aqueous alkali-soluble acrylic resins.
Wherein the acid value of Neocryl BT-24 is 73 mgKOH/g and the acid value of Neocryl BT-21 is 90 mgKOH/g.
In one embodiment, the epoxy group-containing unsaturated compound includes at least one of glycidyl acrylate, glycidyl methacrylate, α -n-propyl glycidyl acrylate, β -ethyl glycidyl methacrylate; and/or
The unsaturated compound containing ethoxy comprises at least one of ethoxylated trimethylolpropane triacrylate and polyethylene glycol diacrylate.
In one embodiment, the photoinitiator is at least one of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 4-isopropylthioxanthone, 1-hydroxycyclohexylphenyl methanone, bis 2, 6-difluoro-3-pyrrolophenyltitanocene, triphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenyl phosphonate, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide; and/or
The solvent comprises at least one of dimethyl oxalate, diethyl oxalate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dipropyl adipate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, terpineol, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate.
In one embodiment, the dispersant comprises at least one of a polyester-based dispersant, a polyether-based dispersant; and/or
The leveling agent comprises at least one of acrylic polysiloxane, polyether modified polysiloxane, polysiloxane polyether copolymer and polysiloxane; and/or
The defoamer comprises at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate and organic silicon resin.
In one embodiment, the method for preparing the modifying additive comprises the following steps:
(1) Uniformly mixing barium titanate and aluminum ammonium sulfate, calcining for 2-8 hours at 1100-1200 ℃, and ball milling to obtain barium titanate coated with aluminum oxide;
(2) Adding cashew nut shell oil dihydric alcohol, an isocyanate silane coupling agent and a catalyst into a reaction kettle, reacting for 4-12 hours at 55-70 ℃ under the protection of nitrogen, and filtering to obtain a modifier;
(3) Adding the modifier into an organic solvent, dispersing uniformly, adding barium titanate wrapped by alumina, performing ultrasonic treatment at 55-65 ℃ for 2-6 hours, filtering, and drying to obtain the modified additive.
According to the invention, barium titanate and aluminum ammonium sulfate are uniformly mixed, and then the mixture is calcined for 2-8 hours at 1100-1200 ℃, aluminum ammonium sulfate is completely decomposed into aluminum oxide in the calcining process, aluminum oxide generated by decomposition is coated on the surface of barium titanate, then a modifier is synthesized through cashew nut shell oil dihydric alcohol and an isocyanate silane coupling agent, and the barium titanate coated with aluminum oxide is modified by using a specific modifier, so that the dispersion performance of the barium titanate is effectively improved, the barium titanate can be uniformly dispersed in a system, the compatibility with an organic carrier is excellent, the glass powder can be effectively wetted and filled, the dielectric constant is remarkably reduced, and meanwhile, the coated aluminum oxide can reduce the crystallization tendency of the glass powder to a certain extent, improve the chemical stability, the mechanical strength and the hardness and improve the thermal stability.
In one embodiment, the mass ratio of the barium titanate to the aluminum ammonium sulfate is 1: (0.2 to 0.6); and/or
The inventors of the present invention found that the mass ratio of barium titanate to aluminum ammonium sulfate has a large influence on the performance by controlling the mass ratio of barium titanate to aluminum ammonium sulfate to 1: preferably in the range of (0.2-0.6), if the aluminum ammonium sulfate is too much (i.e. the mass ratio is larger than 1:0.6), the aluminum oxide is excessively introduced, on one hand, the aluminum oxide film is too thick, so that the reduction of the dielectric constant is affected, on the other hand, the aluminum oxide is too much, the surface is striped, the viscosity of the system is increased, the melting and clarification are difficult, the crystallization tendency is increased, and if the aluminum oxide is excessively introduced (i.e. the mass ratio is smaller than 1:0.2), the improvement range of the performance is limited.
The mass ratio of the cashew nut shell oil dihydric alcohol to the isocyanate silane coupling agent to the catalyst is (1-4): 1: (0.02-0.08).
In one embodiment, the mass ratio of the modifier, the solvent and the barium titanate coated by alumina is 1: (5-20): (2-10).
In one embodiment, the isocyanatosilane coupling agent comprises at least one of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl methyl dimethoxysilane;
the catalyst comprises an organobismuth catalyst;
the organic solvent comprises at least one of methanol, ethanol and acetone.
Exemplary, glassThe glass powder comprises the following components in percentage by mass: 45-55% silicon dioxide (SiO) 2 ) 18-25% boron oxide (B) 2 O 3 ) 12-20% bismuth oxide (Bi) 2 O 3 ) 4-6% sodium oxide (Na) 2 O), 0.8 to 1.5% of zirconia (ZrO) 2 ) 0.1 to 0.4% of titanium dioxide (TiO) 2 ）。
According to the invention, the glass powder which can stably exist in medium slurry and weak acid environment is obtained by combining the silicon dioxide, the boron oxide, the bismuth oxide, the sodium oxide, the zirconium oxide and the cobalt oxide according to the specific mass percentages, and the glass powder does not contain alkali metal and alkaline earth metal, has excellent chemical stability, and has good dispersibility, low sintering temperature, excellent insulating property and can be well used as the medium slurry.
An embodiment of the present invention provides a method for preparing a medium slurry, including the steps of:
uniformly mixing photosensitive resin, photo-curing prepolymer, photo-curing monomer, photo-initiator, solvent, leveling agent, defoaming agent and dispersing agent to obtain an organic carrier;
mixing the organic carrier, the glass powder and the modifying additive uniformly, grinding and filtering to obtain the medium slurry.
The following examples are provided to facilitate an understanding of the present invention. These examples are not provided to limit the scope of the claims.
Example 1
The medium slurry comprises the following components in percentage by mass: 18% of organic carrier, 76% of glass powder and 6% of modifying additive.
The organic carrier comprises the following components in percentage by mass: 63% of photosensitive resin, 4% of glycidyl methacrylate, 4% of hydroxyethyl methacrylate, 4% of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), 23% of dimethyl oxalate, 0.5% of TEGO 270 leveling agent, 0.5% of tributyl phosphate and 1% of Hypermer KD-1 dispersing agent.
The photosensitive resin is Neocryl BT-24 which is the product model of aqueous alkali-soluble acrylic resin.
The preparation method of the modified additive comprises the following steps:
(1) Barium titanate and aluminum ammonium sulfate are mixed according to the mass ratio of 1:0.4 is placed in a V-shaped mixer, uniformly stirred at 600rpm to obtain a mixture, and then the mixture is calcined in a muffle furnace at 1150 ℃ for 5 hours, taken out, cooled and ball-milled at 500rpm for 4 hours to obtain barium titanate coated with alumina;
(2) Cashew nut shell oil glycol, 3-isocyanatopropyl triethoxysilane and an organobismuth catalyst (DY-20) are mixed according to the mass ratio of 2:1:0.05 is added into a reaction kettle, reacted for 8 hours at 65 ℃ under the protection of nitrogen, and filtered to obtain a modifier;
(3) Adding the modifier into acetone, dispersing uniformly, adding barium titanate wrapped by alumina, performing ultrasonic treatment at 60 ℃ for 5 hours by 500W, filtering, and drying to obtain a modified additive; wherein the mass ratio of the modifier to the solvent to the barium titanate coated by the aluminum oxide is 1:10:4.
wherein, cashew shell oil glycol product model FX-9203LP.
The glass powder comprises the following components in percentage by mass: 52% silica, 24% boron oxide, 18% bismuth oxide, 5% sodium oxide, 0.9% zirconium oxide, 0.1% titanium dioxide.
The preparation method of the glass powder comprises the following steps:
(1) Adding silicon dioxide, boron oxide, bismuth oxide, sodium oxide, zirconium oxide and titanium dioxide into a V-shaped mixer, and uniformly mixing to obtain a mixture;
(2) Putting the mixture into a corundum crucible, and then putting the corundum crucible into a high-temperature furnace for smelting, wherein the smelting temperature is 1500 ℃, and the smelting time is 4 hours, so as to obtain glass liquid;
(3) And (3) placing the glass liquid in a stainless steel mold for cooling and molding, placing in a muffle furnace for annealing at 650 ℃ for 3 hours, cooling to room temperature along with the furnace, crushing into powder, and grinding to the particle size of 1 micrometer to obtain glass powder.
The preparation method of the medium slurry comprises the following steps:
uniformly mixing photosensitive resin, photo-curing prepolymer, photo-curing monomer, photo-initiator, solvent, leveling agent, defoaming agent and dispersing agent to obtain an organic carrier;
mixing the organic carrier, the glass powder and the modifying additive uniformly, grinding and filtering to obtain the medium slurry.
Example 2
The medium slurry comprises the following components in percentage by mass: 10% of organic carrier, 80% of glass powder and 10% of modifying additive.
The organic carrier comprises the following components in percentage by mass: 60% of photosensitive resin, 5% of glycidyl methacrylate, 5% of hydroxyethyl methacrylate, 5%1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), 23% of dimethyl oxalate, 0.5% of TEGO 270 leveling agent, 0.5% of tributyl phosphate and 1% of Hypermer KD-1 dispersing agent.
The photosensitive resin is Neocryl BT-21 which is the product model of aqueous alkali-soluble acrylic resin.
The preparation method of the modified additive comprises the following steps:
(1) Barium titanate and aluminum ammonium sulfate are mixed according to the mass ratio of 1: placing 0.2 in a V-shaped mixer, uniformly stirring at 600rpm to obtain a mixture, calcining the mixture in a muffle furnace at 1150 ℃ for 5 hours, taking out, cooling, and ball-milling at 500rpm for 4 hours to obtain barium titanate coated with alumina;
(2) Cashew nut shell oil glycol, 3-isocyanatopropyl triethoxysilane and an organobismuth catalyst (DY-20) are mixed according to the mass ratio of 3:1:0.04 is added into a reaction kettle, reacted for 8 hours at 65 ℃ under the protection of nitrogen, and filtered to obtain a modifier;
(3) Adding the modifier into acetone, dispersing uniformly, adding barium titanate wrapped by alumina, performing ultrasonic treatment at 60 ℃ for 5 hours by 500W, filtering, and drying to obtain a modified additive; wherein the mass ratio of the modifier to the solvent to the barium titanate coated by the aluminum oxide is 1:8:3.
wherein, cashew shell oil glycol product model FX-9203LP.
The glass powder comprises the following components in percentage by mass: 52% silica, 24% boron oxide, 18% bismuth oxide, 5% sodium oxide, 0.9% zirconium oxide, 0.1% titanium dioxide.
The preparation method of the glass powder comprises the following steps:
(1) Adding silicon dioxide, boron oxide, bismuth oxide, sodium oxide, zirconium oxide and titanium dioxide into a V-shaped mixer, and uniformly mixing to obtain a mixture;
(2) Putting the mixture into a corundum crucible, and then putting the corundum crucible into a high-temperature furnace for smelting, wherein the smelting temperature is 1500 ℃, and the smelting time is 4 hours, so as to obtain glass liquid;
(3) And (3) placing the glass liquid in a stainless steel mold for cooling and molding, placing in a muffle furnace for annealing at 650 ℃ for 3 hours, cooling to room temperature along with the furnace, crushing into powder, and grinding to the particle size of 1 micrometer to obtain glass powder.
The preparation method of the medium slurry comprises the following steps:
uniformly mixing photosensitive resin, photo-curing prepolymer, photo-curing monomer, photo-initiator, solvent, leveling agent, defoaming agent and dispersing agent to obtain an organic carrier;
mixing the organic carrier, the glass powder and the modifying additive uniformly, grinding and filtering to obtain the medium slurry.
Example 3
The medium slurry comprises the following components in percentage by mass: 20% of organic carrier, 77% of glass powder and 3% of modifying additive.
The organic carrier comprises the following components in percentage by mass: 66% of photosensitive resin, 3% of glycidyl methacrylate, 3% of hydroxyethyl methacrylate, 3%1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), 23% of dimethyl oxalate, 0.5% of TEGO 270 leveling agent, 0.5% of tributyl phosphate and 1% of Hypermer KD-1 dispersing agent.
The photosensitive resin is Neocryl BT-24 which is the product model of aqueous alkali-soluble acrylic resin.
The preparation method of the modified additive comprises the following steps:
(1) Barium titanate and aluminum ammonium sulfate are mixed according to the mass ratio of 1: placing 0.6 in a V-shaped mixer, uniformly stirring at 600rpm to obtain a mixture, calcining the mixture in a muffle furnace at 1150 ℃ for 5 hours, taking out, cooling, and ball-milling at 500rpm for 4 hours to obtain barium titanate coated with alumina;
(2) Cashew nut shell oil glycol, 3-isocyanatopropyl triethoxysilane and an organobismuth catalyst (DY-20) are mixed according to the mass ratio of 4:1:0.05 is added into a reaction kettle, reacted for 8 hours at 65 ℃ under the protection of nitrogen, and filtered to obtain a modifier;
(3) Adding the modifier into acetone, dispersing uniformly, adding barium titanate wrapped by alumina, performing ultrasonic treatment at 60 ℃ for 5 hours by 500W, filtering, and drying to obtain a modified additive; wherein the mass ratio of the modifier to the solvent to the barium titanate coated by the aluminum oxide is 1:15:5.
wherein, cashew shell oil glycol product model FX-9203LP.
The glass powder comprises the following components in percentage by mass: 52% silica, 24% boron oxide, 18% bismuth oxide, 5% sodium oxide, 0.9% zirconium oxide, 0.1% titanium dioxide.
The preparation method of the glass powder comprises the following steps:
(1) Adding silicon dioxide, boron oxide, bismuth oxide, sodium oxide, zirconium oxide and titanium dioxide into a V-shaped mixer, and uniformly mixing to obtain a mixture;
(2) Putting the mixture into a corundum crucible, and then putting the corundum crucible into a high-temperature furnace for smelting, wherein the smelting temperature is 1500 ℃, and the smelting time is 4 hours, so as to obtain glass liquid;
(3) And (3) placing the glass liquid in a stainless steel mold for cooling and molding, placing in a muffle furnace for annealing at 650 ℃ for 3 hours, cooling to room temperature along with the furnace, crushing into powder, and grinding to the particle size of 1 micrometer to obtain glass powder.
The preparation method of the medium slurry comprises the following steps:
uniformly mixing photosensitive resin, photo-curing prepolymer, photo-curing monomer, photo-initiator, solvent, leveling agent, defoaming agent and dispersing agent to obtain an organic carrier;
mixing the organic carrier, the glass powder and the modifying additive uniformly, grinding and filtering to obtain the medium slurry.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 uses barium titanate instead of the modifying additive, all other things being equal.
The medium slurry comprises the following components in percentage by mass: 18% of organic carrier, 76% of glass powder and 6% of barium titanate.
Comparative example 2
Comparative example 2 is different from example 1 in that barium titanate and aluminum ammonium sulfate are different in mass ratio, and the mass ratio of barium titanate to aluminum ammonium sulfate in this comparative example is 1:0.1, all others being identical.
Comparative example 3
Comparative example 3 is different from example 1 in that barium titanate and aluminum ammonium sulfate are different in mass ratio, and the mass ratio of barium titanate to aluminum ammonium sulfate in this comparative example is 1:1, all others being identical.
Comparative example 4
Comparative example 4 differs from example 1 in that the photosensitive resin is different and the other are the same.
In the comparative example, epoxy acrylic resin is used as photosensitive resin, the product model of the epoxy acrylic resin is WDS-1161, and the acid value is 85-95 mgKOH/g.
Comparative example 5
Comparative example 5 differs from example 1 in that the glass frit of comparative example 5 was a Ca-Si-Zn-Al system glass frit, all of which were identical.
The Ca-Si-Zn-Al system glass powder comprises the following components in percentage by mass: 30% of calcium oxide, 27% of silicon dioxide, 15% of zinc oxide, 10% of aluminum oxide and 18% of boron oxide.
Comparative example 6
Comparative example 5 differs from example 1 in that the glass frit of comparative example 5 was a Ca-Si-Zn-Al system glass frit, all of which were identical.
The Ba-Si-Zn-Ca system glass powder comprises the following components in percentage by mass: 12% of barium oxide, 40% of silicon dioxide, 30% of zinc oxide, 12% of calcium oxide, 5% of zirconium oxide and 1% of phosphorus pentoxide.
Test case
The screen printing conditions were: printing a 360-mesh stainless steel screen; the drying conditions are as follows: 140 ℃ for 20 minutes; the exposure conditions were: 500mj energy, 20um opening film mask; the conditions of the developing solution are as follows: na (Na) 2 CO 3 The development pressure of the aqueous solution was 0.2kg (as shown in FIG. 1).
The properties of the cured slurries were tested.
1. The substrate was placed in an aqueous hydrochloric acid (weak acid) at pH 5 and held for 168 hours, and the substrate was subjected to the test results shown in Table 1, with or without flaking, cracking or bubbling.
2. SJ/T11512-2015 related requirements insulation resistance test was performed and the test results are shown in Table 1.
TABLE 1
| Hydrochloric acid soaking for 168h at pH 5 | Insulation resistance (omega) | |
| Example 1 | No change | 1.95×10 13 |
| Example 2 | No change | 9.50×10 12 |
| Example 3 | No change | 9.41×10 12 |
| Comparative example 1 | More cracks appear | 9.28×10 10 |
| Comparative example 2 | Slight cracking occurred | 2.59×10 11 |
| Comparative example 3 | More cracks appear | 1.07×10 11 |
| Comparative example 4 | Slight cracking occurred | 1.57×10 12 |
| Comparative example 5 | Slight cracking occurred | 2.15×10 11 |
| Comparative example 6 | Slight cracking occurred | 2.09×10 11 |
As can be seen from table 1, the slurries of the present invention have excellent chemical stability and insulation properties.
Example 1 is the best mode of carrying out the invention and has the best performance.
As can be seen from comparative examples 1 and 1 to 3, the modified additive of the present invention can significantly improve chemical stability and insulation performance, and the mass ratio of barium titanate to aluminum ammonium sulfate has a large influence on chemical stability and insulation performance, and the mass ratio of the two needs to be strictly controlled within the scope of the present invention.
As is clear from comparative examples 1 and 4, the photosensitive resin of the present invention can further improve chemical stability and insulation properties.
As can be seen from comparative examples 1 and 5 to 6, the glass frit according to the present invention can significantly improve chemical stability and insulation properties as compared with conventional glass frits in the world.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The medium slurry is characterized by comprising the following components in percentage by mass: 10-20% of organic carrier, 60-80% of glass powder and 1-10% of modifying additive;
the organic carrier comprises the following components in percentage by mass: 50-70% of photosensitive resin, 3-5% of photo-curing prepolymer, 3-5% of photo-curing monomer, 3-5% of photoinitiator, 15-25% of solvent, 0.3-2% of flatting agent, 0.3-2% of defoaming agent and 0.3-2% of dispersing agent;
the molecular structure of the photosensitive resin contains photosensitive groups and alkali-soluble groups;
the photo-curing prepolymer is at least one of unsaturated compound containing epoxy group and unsaturated compound containing ethoxy group;
the photo-curing monomer comprises at least one of methyl methacrylate, hexafluorobutyl methacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxylated trimethylolpropane triacrylate and trimethylolpropane triacrylate.
2. The medium paste according to claim 1, wherein the photosensitive resin has an acid value of 70 to 100mgKOH/g, and the photosensitive resin is an aqueous alkali-soluble acrylic resin.
3. The media slurry of claim 1, wherein the epoxy-containing unsaturated compound comprises at least one of glycidyl acrylate, glycidyl methacrylate, α -n-propyl glycidyl acrylate, β -ethyl glycidyl methacrylate; and/or
The unsaturated compound containing ethoxy comprises at least one of ethoxylated trimethylolpropane triacrylate and polyethylene glycol diacrylate.
4. The media slurry of claim 1, wherein the photoinitiator is at least one of 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 4-isopropylthioxanthone, 1-hydroxycyclohexylphenyl methanone, bis 2, 6-difluoro-3-pyrrolophenyltitanocene, triphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide; and/or
The solvent comprises at least one of dimethyl oxalate, diethyl oxalate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dipropyl adipate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, terpineol, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate.
5. The media slurry of claim 1, wherein the dispersant comprises at least one of a polyester-based dispersant, a polyether-based dispersant; and/or
The leveling agent comprises at least one of acrylic polysiloxane, polyether modified polysiloxane, polysiloxane polyether copolymer and polysiloxane; and/or
The defoamer comprises at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate and organic silicon resin.
6. The media slurry of claim 1, wherein the method of preparing the modifying additive comprises the steps of:
(1) Uniformly mixing barium titanate and aluminum ammonium sulfate, calcining for 2-8 hours at 1100-1200 ℃, and ball milling to obtain barium titanate coated with aluminum oxide;
(2) Adding cashew nut shell oil dihydric alcohol, an isocyanate silane coupling agent and a catalyst into a reaction kettle, reacting for 4-12 hours at 55-70 ℃ under the protection of nitrogen, and filtering to obtain a modifier;
(3) Adding the modifier into an organic solvent, dispersing uniformly, adding barium titanate wrapped by alumina, performing ultrasonic treatment at 55-65 ℃ for 2-6 hours, filtering, and drying to obtain the modified additive.
7. The medium slurry according to claim 6, wherein the mass ratio of the barium titanate to the aluminum ammonium sulfate is 1: (0.2 to 0.6); and/or
The mass ratio of the cashew nut shell oil dihydric alcohol to the isocyanate silane coupling agent to the catalyst is (1-4): 1: (0.02-0.08).
8. The medium slurry according to claim 6, wherein the mass ratio of the modifier, the solvent, and the alumina-coated barium titanate is 1: (5-20): (2-10).
9. The media slurry of claim 6, wherein the isocyanatosilane coupling agent comprises at least one of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl methyl dimethoxysilane;
the catalyst comprises an organobismuth catalyst;
the organic solvent comprises at least one of methanol, ethanol and acetone.
10. A method of preparing a media slurry according to any one of claims 1 to 9, comprising the steps of:
uniformly mixing photosensitive resin, photo-curing prepolymer, photo-curing monomer, photo-initiator, solvent, leveling agent, defoaming agent and dispersing agent to obtain an organic carrier;
mixing the organic carrier, the glass powder and the modifying additive uniformly, grinding and filtering to obtain the medium slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310475902.XA CN116206800B (en) | 2023-04-28 | 2023-04-28 | Medium slurry and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310475902.XA CN116206800B (en) | 2023-04-28 | 2023-04-28 | Medium slurry and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116206800A CN116206800A (en) | 2023-06-02 |
| CN116206800B true CN116206800B (en) | 2023-07-21 |
Family
ID=86517665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310475902.XA Active CN116206800B (en) | 2023-04-28 | 2023-04-28 | Medium slurry and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116206800B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116543949B (en) * | 2023-07-04 | 2023-12-22 | 乾宇微纳技术(深圳)有限公司 | Hole filling slurry and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278638A (en) * | 2000-03-30 | 2001-10-10 | Toray Ind Inc | Photosensitive glass paste and plasma display using it |
| CN101481557A (en) * | 2008-01-09 | 2009-07-15 | 王广武 | Colored powdered glass printing ink, oil paint and coating |
| JP2010044259A (en) * | 2008-08-14 | 2010-02-25 | Jsr Corp | Photosensitive paste composition and pattern forming method |
| CN101727005A (en) * | 2009-05-25 | 2010-06-09 | 四川虹欧显示器件有限公司 | Photosensitive resin composition for plasma panel electrode |
| JP2011076898A (en) * | 2009-09-30 | 2011-04-14 | Taiyo Holdings Co Ltd | Photosensitive conductive paste and method for manufacturing the same |
| CN102365690A (en) * | 2009-03-31 | 2012-02-29 | 太阳控股株式会社 | Photosensitive electrically conductive paste and electrode pattern |
| CN110998443A (en) * | 2017-08-03 | 2020-04-10 | 昭和电工株式会社 | Photosensitive resin composition and method for producing same |
| CN113571228A (en) * | 2021-07-02 | 2021-10-29 | 浙江晶科新材料有限公司 | Front conductive silver paste for crystalline silicon solar cell and preparation method thereof |
| CN113903497A (en) * | 2021-12-09 | 2022-01-07 | 西安宏星电子浆料科技股份有限公司 | Isolation medium slurry and preparation method thereof |
| CN115083656A (en) * | 2022-06-22 | 2022-09-20 | 深圳市化讯半导体材料有限公司 | Photosensitive silver paste and preparation method and application thereof |
| CN115677939A (en) * | 2022-11-25 | 2023-02-03 | 茂名清荷科技有限公司 | Photosensitive graft polymer and photosensitive resin composition containing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172693A4 (en) * | 2000-01-25 | 2006-04-05 | Daicel Chem | Photocurable resin compositions |
-
2023
- 2023-04-28 CN CN202310475902.XA patent/CN116206800B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278638A (en) * | 2000-03-30 | 2001-10-10 | Toray Ind Inc | Photosensitive glass paste and plasma display using it |
| CN101481557A (en) * | 2008-01-09 | 2009-07-15 | 王广武 | Colored powdered glass printing ink, oil paint and coating |
| JP2010044259A (en) * | 2008-08-14 | 2010-02-25 | Jsr Corp | Photosensitive paste composition and pattern forming method |
| CN102365690A (en) * | 2009-03-31 | 2012-02-29 | 太阳控股株式会社 | Photosensitive electrically conductive paste and electrode pattern |
| CN101727005A (en) * | 2009-05-25 | 2010-06-09 | 四川虹欧显示器件有限公司 | Photosensitive resin composition for plasma panel electrode |
| JP2011076898A (en) * | 2009-09-30 | 2011-04-14 | Taiyo Holdings Co Ltd | Photosensitive conductive paste and method for manufacturing the same |
| CN110998443A (en) * | 2017-08-03 | 2020-04-10 | 昭和电工株式会社 | Photosensitive resin composition and method for producing same |
| CN113571228A (en) * | 2021-07-02 | 2021-10-29 | 浙江晶科新材料有限公司 | Front conductive silver paste for crystalline silicon solar cell and preparation method thereof |
| CN113903497A (en) * | 2021-12-09 | 2022-01-07 | 西安宏星电子浆料科技股份有限公司 | Isolation medium slurry and preparation method thereof |
| CN115083656A (en) * | 2022-06-22 | 2022-09-20 | 深圳市化讯半导体材料有限公司 | Photosensitive silver paste and preparation method and application thereof |
| CN115677939A (en) * | 2022-11-25 | 2023-02-03 | 茂名清荷科技有限公司 | Photosensitive graft polymer and photosensitive resin composition containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116206800A (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116206800B (en) | Medium slurry and preparation method thereof | |
| CN113461427B (en) | Photocuring 4D printing ceramic-based precursor slurry, ceramic part and preparation method | |
| KR20210149026A (en) | Water-based epoxy floor paint and method for manufacturing the same | |
| CN1703458A (en) | Sealant composition for liquid crystal and process for producing liquid-crystal display panel with the same | |
| CN110803915A (en) | Ceramic photocuring material and preparation method thereof | |
| WO2013089413A1 (en) | Hard coating composition | |
| CN109575646A (en) | Aluminium pigment and preparation method thereof | |
| CN109765756A (en) | Photosensitive composition, colour filter and display device | |
| CN101875832A (en) | Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent | |
| JPH1192168A (en) | Glass composition for photosensitive glass paste | |
| CN113603467A (en) | Photocuring ceramic slurry for 3D printing and pretreatment method of formed blank | |
| CN112086254B (en) | Environment-friendly thick-film resistor paste | |
| JP4573696B2 (en) | Photosensitive composition | |
| CN102385254B (en) | Photo-sensitivity resin composition | |
| CN115772033A (en) | Method for preparing zirconium oxide ceramic material by DLP technology and zirconium oxide ceramic material | |
| CN113817139B (en) | Solvent-free alkali development photosensitive resin and application thereof in hole plugging ink | |
| CN108333871A (en) | Photosensitive composition, colour filter and the display device comprising it | |
| CN116543949B (en) | Hole filling slurry and preparation method thereof | |
| CN112939595A (en) | Microwave dielectric ceramic material with near-zero temperature coefficient at high temperature and preparation method thereof | |
| CN117303870A (en) | Zero-sintering shrinkage aluminum-based ceramic core material manufactured by photocuring additive | |
| CN115975457B (en) | Water-based paint composition and preparation method thereof | |
| CN115925421B (en) | Photo-curing 3D printing mechanoluminescence ceramic and preparation method and application thereof | |
| CN116621612B (en) | Composition for preparing ceramic overglaze, ceramic brick with mold texture, and preparation method and application thereof | |
| CN117070133B (en) | Wear-resistant anticorrosive paint and preparation method thereof | |
| JPH0274555A (en) | Ceramic green sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230802 Address after: 518000, Building 514-2, Hengtai Yu Building, Tangwei Community, Fenghuang Street, Guangming District, Shenzhen City, Guangdong Province Patentee after: Qianyu Micro Nano Technology (Shenzhen) Co.,Ltd. Patentee after: Qianyu Electronic Materials (Suzhou) Co.,Ltd. Patentee after: Qianyu electronic materials (Dongguan) Co.,Ltd. Address before: 518000, Building 514-2, Hengtai Yu Building, Tangwei Community, Fenghuang Street, Guangming District, Shenzhen City, Guangdong Province Patentee before: Qianyu Micro Nano Technology (Shenzhen) Co.,Ltd. |
|
| TR01 | Transfer of patent right |