CN111511686A - Modified perovskite-type composite oxide, method for producing same, and composite dielectric material - Google Patents
Modified perovskite-type composite oxide, method for producing same, and composite dielectric material Download PDFInfo
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- CN111511686A CN111511686A CN201880082164.XA CN201880082164A CN111511686A CN 111511686 A CN111511686 A CN 111511686A CN 201880082164 A CN201880082164 A CN 201880082164A CN 111511686 A CN111511686 A CN 111511686A
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Abstract
A modified perovskite-type composite oxide in which the surface of perovskite-type composite oxide particles is coated with a silane coupling agent represented by the following general formula (1). (XY)aSi(OZ)4‑a(1) (in the general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth) acrylic group, an isocyanate group or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, Z is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an ethylene groupAcyl or C2-C4 alkoxyalkyl, and a is 1 or 2. ).
Description
Technical Field
The present invention relates to a modified perovskite-type composite oxide useful as a composite dielectric or an inorganic filler for a composite piezoelectric body, a method for producing the same, and a composite dielectric material containing the modified perovskite-type composite oxide.
Background
In recent years, in the high electronic control in the electronics industry, ceramic sintered bodies obtained by molding ceramic powder and then firing the ceramic powder have been used in many cases as passive devices requiring high performance. The processing of circuits and the mounting of components are complicated, and are also required to be low in cost, space-saving, high in speed, and highly reliable. Under such a background, the size, shape, mounting, and the like of the ceramic sintered body are greatly restricted by the molding method. Further, since the sintered body has high hardness and is brittle, it is difficult to freely process the sintered body, and it is extremely difficult to obtain an arbitrary shape or a complicated shape.
Therefore, a composite dielectric material in which an inorganic filler, which is broadly called a dielectric, such as a ferroelectric, a pyroelectric body, or a piezoelectric body, is dispersed in a resin has been attracting attention as a novel material which is excellent in processability and has various functions such as high dielectric characteristics, low loss characteristics, pyroelectric characteristics, and piezoelectric characteristics.
As an inorganic filler used in the above, for example, a perovskite type composite oxide is known (for example, see patent document 1). However, the perovskite-type composite oxide has a problem that the specific surface area changes with time to degrade the dielectric characteristics, and also has a problem that an a-site metal such as Ba, Ca, Sr, Mg, or the like in the structure is eluted when the perovskite-type composite oxide is brought into contact with water, and thus interface separation between the resin and the inorganic filler occurs, or insulation deterioration occurs due to ion migration.
On the other hand, as described in patent documents 2 to 4, it is known that an inorganic filler such as barium titanate is surface-treated with a coupling agent in order to improve dispersibility in a resin.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2005/093763
Patent document 2: japanese laid-open patent publication No. 2003-49092
Patent document 3: japanese patent laid-open publication No. 2005-15652
Patent document 4: japanese laid-open patent publication No. 7-240117
Patent document 5: japanese patent laid-open publication No. 2007-308345
Patent document 6: japanese patent laid-open publication No. 2017-19938
Disclosure of Invention
Technical problem to be solved by the invention
However, the inventors of the present invention have studied and found that the surface of perovskite-type composite oxide particles is treated with only a coupling agent, and the change over time in the specific surface area and the elution of a-site metal such as Ba cannot be sufficiently reduced, and there is still room for improvement in the miscibility with a resin. Good dispersibility in an organic solvent is indispensable for uniform filling properties into a resin and affinity with a resin, and it is difficult to obtain sufficient dispersion in an organic solvent without treating the perovskite-type composite oxide or even by surface treatment with a conventional coupling agent.
Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a perovskite-type composite oxide excellent in filling properties and dispersibility into a resin, and a method for producing the same.
Technical solution for solving technical problem
The present inventors have conducted extensive studies in view of the above circumstances, and as a result, have found that a perovskite-type composite oxide coated with a specific silane coupling agent is excellent in dispersibility in an organic solvent and excellent in filling properties and dispersibility into a resin, and have completed the present invention.
That is, the present invention is a modified perovskite-type composite oxide characterized by being obtained by coating the surface of perovskite-type composite oxide particles with a silane coupling agent represented by the following general formula (1).
(XY)aSi(OZ)4-a(1)
(in the general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth) acrylic group, an isocyanate group or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, Z is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group or an alkoxyalkyl group having 2 to 4 carbon atoms, and a is 1 or 2.)
The present invention is also a process for producing a modified perovskite-type composite oxide, which comprises mixing a perovskite-type composite oxide with a silane coupling agent represented by the general formula (1) above, feeding the mixture to a jet mill, and coating the surface of perovskite-type composite oxide particles with the silane coupling agent while pulverizing the perovskite-type composite oxide.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a modified perovskite-type composite oxide excellent in filling properties and dispersibility into a resin, and a method for producing the same.
Drawings
Fig. 1 shows the results of measuring the particle size distribution of the modified barium titanate particles obtained in example 1 in an organic solvent.
FIG. 2 shows the results of the measurement of the particle size distribution of barium titanate particles in an organic solvent obtained in comparative example 1.
FIG. 3 shows the results of the particle size distribution measurement of barium titanate particles in water obtained in comparative example 1.
Detailed Description
< modified perovskite-type composite oxide >
The modified perovskite-type composite oxide of the present invention is a perovskite-type composite oxide particle surface-coated with a silane coupling agent represented by the following general formula (1).
(XY)aSi(OZ)4-a(1)
(in the general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth) acrylic group, an isocyanate group or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, Z is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group or an alkoxyalkyl group having 2 to 4 carbon atoms, and a is 1 or 2.)
The perovskite-type composite oxide to be modified is not particularly limited, and examples thereof include barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, potassium sodium lithium niobate, bismuth potassium titanate, bismuth sodium titanate, bismuth ferrite, potassium tantalate, and composite solid solutions thereof, such as potassium tantalate niobate and potassium sodium lithium tantalate. These perovskite-type composite oxides may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The production process of such a perovskite-type composite oxide is not particularly limited, and for example, a material obtained by a known method such as a wet method including a coprecipitation method, a hydrolysis method, a hydrothermal synthesis method, a sol-gel method, and a solid phase method can be used. The physical properties of these perovskite-type composite oxides are not particularly limited, and the BET specific surface area is preferably 0.2m2/g～20m2A ratio of 0.3 m/g2/g～15m2In the case of/g, it is preferable from the viewpoint of treatment in the pulverization step. The average particle diameter of the perovskite-type composite oxide is preferably 0.1 to 10 μm, more preferably 0.15 to 5 μm, and is preferable from the viewpoint of handling in the pulverization step. The average particle diameter is a median diameter (D50) measured by a laser diffraction scattering method using water as a dispersion medium.
The particle shape of the perovskite-type composite oxide to be modified is not particularly limited, and may be any shape such as a sphere, a granule, a plate, a scale, a whisker, a rod, or a filament.
In the general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth) acrylic group, an isocyanate group or a mercapto group. Among these, from the viewpoint of imparting dispersibility in a general organic solvent, a hydrogen atom is preferable.
In the general formula (1), examples of the linear alkylene group having 5 or more carbon atoms represented by Y include n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadecylene and the like. From the viewpoint of ease of handling, the number of carbon atoms of the linear alkylene group is preferably 5 to 20.
In the general formula (1), examples of the alkyl group having 1 to 3 carbon atoms represented by Z include a methyl group, an ethyl group, and a propyl group. In the general formula (1), examples of the alkoxyalkyl group having 2 to 4 carbon atoms represented by Z include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.
Specific examples of the silane coupling agent represented by the general formula (1) include hexyltrimethoxysilane (X ═ hydrogen, Y ═ n-hexylene, Z ═ methyl, a ═ 1), heptyltrimethoxysilane (X ═ hydrogen, Y ═ n-heptylene, Z ═ methyl, a ═ 1), octyltriethoxysilane (X ═ hydrogen, Y ═ n-octylene, Z ═ ethyl, a ═ 1), nonyltrimethoxysilane (X ═ hydrogen, Y ═ n-nonylene, Z ═ methyl, a ═ 1), decyltrimethoxysilane (X ═ hydrogen, Y ═ n-decylene, Z ═ methyl, a ═ 1) undecyltrimethoxysilane (X ═ hydrogen, Y ═ n-undecylene, Z ═ methyl, a ═ 1), dodecyltrimethoxysilane (X ═ hydrogen, Y ═ n-dodecyltrimethoxysilane, Y ═ dodecyltrimethoxysilane, Z ═ n-dodecyltrimethoxysilane, Z ═ tridecyl, Y ═ 1, Y ═ tridecyl, Z ═ methyl, a ═ 1), tetradecyltrimethoxysilane (X ═ hydrogen, Y ═ n-tetradecyl, Z ═ methyl, a ═ 1), pentadecyltrimethoxysilane (X ═ hydrogen, Y ═ n-pentadecyl, Z ═ methyl, a ═ 1), and the like. Among these, hexyltrimethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of imparting dispersibility in a general organic solvent.
When the average particle diameter (D50) of the modified perovskite-type composite oxide of the present invention (perovskite-type composite oxide coated with the silane coupling agent represented by general formula (1)) measured by a laser diffraction scattering method using an organic solvent as a dispersion medium is Dos and the average particle diameter (D50) of the unmodified perovskite-type composite oxide (perovskite-type composite oxide before modification) measured by a laser diffraction scattering method using water as a dispersion medium is Dw, the degree of aggregation represented by Dos/Dw is preferably 1.4 or less, more preferably 1.2 or less. When the degree of aggregation is 1.4 or less, it means that the perovskite-type composite oxide having relatively good wettability with water can be treated in a dispersed state even in an organic solvent. The organic solvent used here is not particularly limited, and examples thereof include methyl ethyl ketone, acetone, n-hexane, methanol, ethanol, toluene, and cyclopentanone.
The modified perovskite-type composite oxide of the present invention preferably has a moisture absorption amount of 0.3 mass% or less, more preferably 0.25 mass% or less. When the moisture content of moisture absorption is 0.3 mass% or less, the degree of change of the surface of the perovskite-type composite oxide as a base material into a hydroxide or a carbonate due to moisture is low, and the change of the particle shape and the deterioration of the electrical characteristics can be prevented. In the present specification, the moisture absorption amount of the modified perovskite-type composite oxide is determined by the following method.
First, a sample of the modified perovskite-type composite oxide immediately after production was precisely weighed (a), and a dried product obtained by heating the sample at 105 ℃ for 2 hours by a shelf dryer was precisely weighed (B). Separately from this, a modified perovskite-type composite oxide sample immediately after production was precisely weighed (a), and a hygroscopic sample obtained by allowing the sample to stand for 180 minutes in an environment of 40 ℃ and 90% humidity to absorb moisture was precisely weighed (c). The dried product obtained by heating the moisture-absorbed sample at 105 ℃ for 2 hours by a shelf dryer was precisely weighed (b). The amount of moisture attached was obtained by the following equation, and the amount of moisture absorbed by the sample was defined as mass%.
Moisture absorption amount (% by mass) (((c-B)/a) × 100) - (((a-B)/a) × 100)
The modified perovskite-type composite oxide of the present invention can be produced by mixing a perovskite-type composite oxide to be modified with a silane coupling agent represented by the above general formula (1), feeding the mixture to a jet mill, and coating the surface of perovskite-type composite oxide particles with the silane coupling agent while pulverizing the perovskite-type composite oxide. By supplying a mixture of the perovskite-type composite oxide and the silane coupling agent represented by the general formula (1) to the jet mill, a new surface of the perovskite-type composite oxide exposed during the milling process can be coated with the silane coupling agent represented by the general formula (1) quickly, and therefore, the chance of exposure to the ambient environment and contact with moisture can be reduced, and elution of the a-site metal and a change in the specific surface area over time can be suppressed.
The method of mixing the perovskite-type composite oxide and the silane coupling agent is not particularly limited, and there may be mentioned: a method of spraying a silane coupling agent to a perovskite-type composite oxide; a method of dry-mixing a solid silane coupling agent with a perovskite-type composite oxide; and a method in which a liquid silane coupling agent is added to the perovskite-type composite oxide dispersed in an organic solvent, and the mixture is obtained by filtration and drying. The silane coupling agent may be used as it is or as a solution dissolved in an appropriate solvent (alcohols, ketones, ethers, etc.). When the perovskite-type composite oxide and the silane coupling agent are mixed, the mass ratio of the perovskite-type composite oxide to the silane coupling agent is preferably 99.5: 0.5 to 95: 5, and more preferably 99: 1 to 96: 4. When the mass ratio of the perovskite-type composite oxide to the silane coupling agent is 99.5: 0.5 to 95: 5, at least 1 layer of the silane coupling agent film can be formed on the surface of the perovskite-type composite oxide particles. However, even if the silane coupling agent is added in a large amount, the obtained effect is not increased, and therefore, it is economically disadvantageous.
Examples of the air flow type pulverizer include a jet mill, a fluid mill, and a fluid bed pulverizer. Among these, the jet mill is preferable from the viewpoint of less contamination due to a structure in which the blade or the medium is not carried into the pulverization chamber.
The conditions for pulverization by the jet mill are not particularly limited, but the pulverizing pressure is preferably 0.03MPa or more, and more preferably 0.05 to 0.7 MPa. The powder input rate is preferably 4 to 40kg/hr, although it depends on the size of the jet mill. By performing the pulverization under such conditions, the surface of the newly exposed perovskite-type composite oxide can be sufficiently and efficiently coated with the silane coupling agent represented by the above general formula (1).
The modified perovskite-type composite oxide of the present invention obtained in this way is excellent in filling properties and dispersibility into a resin, and therefore a composite dielectric material described later which is excellent in high dielectric characteristics, low loss characteristics, thermoelectric characteristics, piezoelectric characteristics, and the like can be produced. The modified perovskite-type composite oxide of the present invention can be used as a ferroelectric, pyroelectric, or piezoelectric material, but in a broad sense, it is a material including a paraelectric material and collectively referred to as a dielectric material.
< composite dielectric Material >
The composite dielectric material of the present invention contains a polymer material and the above-mentioned modified perovskite-type composite oxide as an inorganic filler. The composite dielectric material of the present invention is preferably a material having a relative permittivity of preferably 15 or more, more preferably 20 or more, by containing the modified perovskite-type composite oxide in an amount of preferably 60% by mass or more, more preferably 70% to 90% by mass in a polymer material described later.
Examples of the polymer material that can be used in the present invention include thermosetting resins, thermoplastic resins, and photosensitive resins.
Examples of the thermosetting resin include known resins such as epoxy resins, phenol resins, polyimide resins, melamine resins, isocyanate resins, bismaleimide resins, addition polymers of bismaleimide resins and diamines, polyfunctional cyanate resins, double-bond-added polyphenylene ether resins, unsaturated polyester resins, polyvinyl benzyl ether resins, polybutadiene resins, and fumarate resins. These thermosetting resins may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Among these thermosetting resins, epoxy resins and polyvinyl benzyl ether resins are preferred in view of the balance among heat resistance, processability, price, and the like.
The epoxy resin used in the present invention is a monomer, oligomer or polymer having at least 2 epoxy groups in 1 molecule, and examples thereof include phenol novolac type epoxy resins, phenol novolac type epoxy resins represented by o-cresol novolac type epoxy resins, phenol resins such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol a and bisphenol F, and/or epoxy resins obtained by epoxidizing novolac resins obtained by condensing or co-condensing naphthol such as α -naphthol, β -naphthol and dihydroxynaphthalene with aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under an acidic catalyst, diglycidyl ethers such as bisphenol a, bisphenol B, bisphenol F, bisphenol S and alkyl-substituted or unsubstituted biphenol, adducts or addition polymers of phenol and dicyclopentadiene or terpenes, glycidyl ester type epoxy resins obtained by reacting polybasic acid such as phthalic acid and dimer acid with epichlorohydrin, glycidyl amine type epoxy resins obtained by reacting polyamine such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, epoxy resins obtained by oxidizing linear epoxy bonds such as peracetic acid, and epoxy resins obtained by using 2 or more epoxy resins alone, or 2 epoxy resins obtained by using alicyclic olefin alone or in combination.
As epoxy resin curing agents, all epoxy resin curing agents known to the person skilled in the art can be used, and in particular: ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc. C2～C20Linear aliphatic diamine(s) such as m-phenylenediamine, p-xylylenediamine, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylsulfone, 4 ' -diaminobicyclohexane, bis (4-aminophenyl) phenylmethane, 1, 5-diaminonaphthalene, m-xylylenediamine, p-xylylenediamine, 1-bis (4-aminophenyl) cyclohexane, dicyandiamideAmines of (a); phenol novolac type phenol resins such as phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, and nonylphenol novolac resin; a phenolic resole resin; polyhydroxystyrene such as polyparahydroxystyrene; phenol resins obtained by co-condensation of carbonyl compounds and phenol compounds in which hydrogen atoms bonded to a benzene ring, a naphthalene ring, or another aromatic ring are substituted with hydroxyl groups, such as phenol aralkyl resins and naphthol aralkyl resins; acid anhydrides, and the like. These can be used alone in 1 kind, also can be combined with 2 or more kinds.
The amount of the epoxy resin curing agent is preferably 0.1 to 10, more preferably 0.7 to 1.3 in terms of equivalent ratio to the epoxy resin.
In the present invention, a known curing accelerator can be used to accelerate the curing reaction of the epoxy resin. Examples of the curing accelerator include: tertiary amine compounds such as 1, 8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole; organic phosphine compounds such as triphenylphosphine and tributylphosphine; phosphonium salts, ammonium salts, and the like. These can be used alone in 1 kind, also can be combined with 2 or more kinds.
The polyvinyl benzyl ether resin used in the present invention is a product obtained from a polyvinyl benzyl ether compound. The polyvinyl benzyl ether compound is preferably a compound represented by the following general formula (2).
In the formula of the general formula (2), R1Represents a methyl group or an ethyl group. R2Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R2The hydrocarbon group is an alkyl group, an aralkyl group, an aryl group, or the like which may have a substituent. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aralkyl group include a benzyl group and the like. Examples of the aryl group include a phenyl group and the like. R3To representA hydrogen atom or a vinylbenzyl group. Wherein R is3The hydrogen atom (2) is derived from the starting compound for synthesizing the compound of the general formula (2), and the molar ratio of the hydrogen atom to vinylbenzyl group is preferably 60: 40 to 0: 100, because the curing reaction can be sufficiently advanced, and the composite dielectric material of the present invention can obtain sufficient dielectric characteristics. n represents an integer of 2 to 4.
The polyvinyl benzyl ether compound may be used by polymerizing only it as a resin material, or may be used by copolymerizing it with another monomer. Examples of the copolymerizable monomer include styrene, vinyltoluene, divinylbenzene, divinylbenzyl ether, allylphenol, allylhydroxybenzene, diallyl phthalate, acrylic esters, methacrylic esters, vinylpyrrolidone, and modified products thereof. The blending ratio of these monomers is 2 to 50% by mass based on the polyvinyl benzyl ether compound.
The polymerization and curing of the polyvinyl benzyl ether compound can be carried out by a known method. Curing can be carried out in the presence or absence of a curing agent. As the curing agent, for example, a known radical polymerization initiator such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl perbenzoate can be used. The amount used is 0 to 10 parts by mass per 100 parts by mass of the polyvinyl benzyl ether compound. The curing temperature varies depending on whether or not a curing agent is used and the type of curing agent, but is preferably 20 to 250 ℃, more preferably 50 to 250 ℃ in order to sufficiently cure the resin.
In addition, hydroquinone, benzoquinone, copper salts, and the like may be added for adjustment of curing.
Examples of the thermoplastic resin include known resins such as (meth) acrylic resins, hydroxystyrene resins, phenol-formaldehyde resins, polyester resins, polyimide resins, nylon resins, and polyether imide resins.
Examples of the photosensitive resin include known photosensitive resins such as photopolymerizable resins and photocrosslinkable resins.
Examples of the photopolymerizable resin used in the present invention include resins containing an acrylic copolymer (photosensitive oligomer) having an ethylenically unsaturated group, a photopolymerizable compound (photosensitive monomer), and a photopolymerization initiator; and resins containing an epoxy resin and a photo cation polymerization initiator. Examples of the photosensitive oligomer include: an oligomer obtained by adding acrylic acid to an epoxy resin; an oligomer obtained by further reacting the resulting product with an acid anhydride; and an oligomer obtained by reacting (meth) acrylic acid with a copolymer containing a (meth) acrylic acid monomer having a glycidyl group; an oligomer obtained by further reacting an acid anhydride with the above-mentioned oligomer; an oligomer obtained by reacting a copolymer containing a (meth) acrylic monomer having a hydroxyl group with glycidyl (meth) acrylate; an oligomer obtained by further reacting an acid anhydride with the above-mentioned oligomer; and oligomers obtained by reacting a (meth) acrylic monomer having a hydroxyl group or a (meth) acrylic monomer having a glycidyl group with a copolymer containing maleic anhydride. These can be used alone in 1 kind, also can be combined with 2 or more kinds.
Examples of the photopolymerizable compound (photosensitive monomer) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, N-dimethylacrylamide, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, and tris (hydroxyethyl) isocyanurate tri (meth) acrylate. These can be used alone in 1 kind, also can be combined with 2 or more kinds.
Examples of the photopolymerization initiator include benzoin and alkyl ethers thereof, benzophenones, acetophenones, anthraquinones, xanthones, thioxanthones, and the like. These can be used alone in 1 kind, also can be combined with 2 or more kinds. These photopolymerization initiators can be used together with known and conventional photopolymerization accelerators such as benzoic acid type and tertiary amine type photopolymerization initiators. Examples of the photo-cationic polymerization initiator include triphenylsulfonium hexafluoroantimonate, diphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, and iron aromatic compound salts of Bronsted acid (Ciba-Geigy Co., CG 24-061). These can be used alone in 1 kind, also can be combined with 2 or more kinds.
The alicyclic epoxy resin may be used in combination with the alicyclic epoxy resin, and examples of the alicyclic epoxy resin include vinylcyclohexene diepoxide, alicyclic diepoxyeacetal, alicyclic diepoxydiadipate, alicyclic diepoxycarboxylate, manufactured by DAICE L chemical industries, EHPE-3150, and the like, and 1 kind of these may be used alone, or 2 or more kinds may be used in combination.
Examples of the photo-crosslinkable resin include a water-soluble polymer, such as dichromate, polyvinyl cinnamate (Kodak KPR), and cyclized rubber-azide (Kodak KTFR). These can be used alone in 1 kind, also can be combined with 2 or more kinds.
The dielectric constant of these photosensitive resins is generally as low as 2.5 to 4.0. Therefore, in order to increase the dielectric constant of the adhesive, a higher dielectric polymer (e.g., sumitomo chemical SDP-E (: 15 <), sumitomo chemical cyano resin (: 18 <), or a high dielectric liquid (e.g., sumitomo chemical SDP-S (: 40 <))) may be added within a range that does not impair the photosensitive characteristics of the photosensitive resin.
In the present invention, the above-mentioned polymer materials may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In the composite dielectric material of the present invention, the amount of the modified perovskite-type composite oxide to be blended is preferably 60 mass% or more, and more preferably 70 to 90 mass% in terms of the proportion in the composite with the resin. The reason is that: when the amount is less than 60% by mass, a sufficient relative dielectric constant tends to be not obtained; on the other hand, if the amount exceeds 90% by mass, the viscosity tends to increase, and dispersibility tends to deteriorate, and sufficient strength may not be obtained when the composite is in a solid state. From the above combination, a material having a relative dielectric constant of preferably 15 or more, more preferably 20 or more is desired.
The composite dielectric material of the present invention may contain other fillers in an amount within a range not impairing the effects of the present invention. Examples of the other filler include fine carbon powder such as acetylene black and ketjen black, fine graphite powder, and silicon carbide.
In the composite dielectric material of the present invention, a curing agent, a glass powder, a polymer additive, a reactive diluent, a polymerization inhibitor, a leveling agent, a wettability modifier, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a mildewproofing agent, a humidity control agent, a dye dissolving agent, a buffer, a chelating agent, a flame retardant, and the like may be added within a range not impairing the effects of the present invention. These additives may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The composite dielectric material of the present invention can be produced by preparing a composite dielectric paste, and removing an organic solvent, a curing reaction, or a polymerization reaction.
The composite dielectric paste contains a resin component, a modified perovskite-type composite oxide, an additive and an organic solvent added as required.
The resin component contained in the composite dielectric paste is a polymerizable compound of a thermosetting resin, a polymer of a thermoplastic resin, and a polymerizable compound of a photosensitive resin. These resin components may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The polymerizable compound is a compound having a polymerizable group, and includes, for example, a precursor polymer before complete curing, a polymerizable oligomer, and a monomer. The polymer is a compound in which the polymerization reaction is substantially completed.
The organic solvent to be added as needed is not particularly limited as long as it is an organic solvent capable of dissolving the resin component, and examples thereof include N-methylpyrrolidone, dimethylformamide, ether, diethyl ether, tetrahydrofuran, dioxane, glycol ether of monohydric alcohol having a linear or branched alkyl group with 1 to 6 carbon atoms, propylene glycol ether, butylene glycol ether, ketone, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, ester, ethyl acetate, butyl acetate, ethylene glycol acetate, methoxypropyl acetate, methoxypropanol, other halogenated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like. These organic solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among these, hexane, heptane, cyclohexane, toluene, and xylene (dixlylene) are preferable.
In the present invention, the composite dielectric paste is used after being adjusted to a desired viscosity. The viscosity of the composite dielectric paste is usually 1,000 to 1,000,000 mPas (25 ℃ C.), and in view of the applicability of the composite dielectric paste, it is preferably 10,000 to 600,000 mPas (25 ℃ C.).
The composite dielectric material of the present invention can be processed into a film, a bulk (bulk) or a molded article having a predetermined shape and used, and in particular, can be used as a thin-film high dielectric film.
In order to produce a composite dielectric film using the composite dielectric material of the present invention, for example, it is sufficient to produce the composite dielectric film by a conventionally known method of using a composite dielectric paste, and an example thereof will be described below.
The composite dielectric paste can be formed into a film by applying the composite dielectric paste to a substrate and then drying the paste. As the substrate, for example, a plastic film whose surface is subjected to a peeling treatment can be used. When the film is formed into a film by coating the film on a plastic film subjected to a peeling treatment, it is generally preferable to use the film after peeling the substrate from the film after the formation. Examples of the plastic film that can be used as the substrate include films such as a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, a polyester film, a polyimide film, an aramid film, Kapton, and polymethylpentene. The thickness of the plastic film used as the substrate is preferably 1 to 100 μm, and more preferably 1 to 40 μm. As the release treatment to be performed on the surface of the base material, a release treatment in which silicone, wax, fluororesin, or the like is applied to the surface is preferably employed.
Alternatively, a metal foil may be used as the base material, and a dielectric film may be formed on the metal foil. In such a case, the metal foil used as the base material can be used as an electrode of the capacitor.
The method for applying the composite dielectric paste to a substrate is not particularly limited, and a general application method can be employed. For example, the coating can be performed by a roll coating method, a spray coating method, a screen method, or the like.
Such a dielectric film can be thermally cured by heating after incorporating a substrate such as a printed circuit board. In addition, when a photosensitive resin is used, patterning can be performed by selective exposure.
The composite dielectric material of the present invention may be formed into a film by extrusion molding, for example, by a rolling method.
The dielectric film obtained by extrusion molding may be formed by extrusion molding on the substrate. When a metal foil is used as the base material, the metal foil may be made of copper, aluminum, brass, nickel, iron, or the like, or may be made of an alloy of these metals, a composite foil, or the like. The metal foil may be subjected to a surface roughening treatment or an adhesive application treatment, if necessary.
In addition, a dielectric film may be formed between the metal foils. In this case, the dielectric film may be formed by applying the composite dielectric paste to the metal foils, placing the metal foils thereon, and drying the metal foils while sandwiching the composite dielectric paste between the metal foils. Alternatively, the dielectric film provided between the metal foils may be formed by extrusion molding so as to be sandwiched between the metal foils.
The composite dielectric material of the present invention can be used as a prepreg by preparing a varnish using the organic solvent, impregnating the varnish with a cloth (cloth) or a nonwoven fabric, and drying the impregnated cloth or nonwoven fabric. The type of cloth or nonwoven fabric that can be used is not particularly limited, and known materials can be used. Examples of the cloth include glass cloth, aramid cloth, carbon cloth, and stretched porous polytetrafluoroethylene. Further, the nonwoven fabric may be an aramid nonwoven fabric, cellophane, or the like. The prepreg can be laminated on an electronic component such as a circuit board and then cured to introduce an insulating layer into the electronic component.
The composite dielectric material of the present invention has a high relative permittivity, and therefore can be suitably used as a dielectric layer of an electronic component, particularly an electronic component such as a printed circuit board, a semiconductor package, a capacitor, an antenna for high frequency, an inorganic E L, and the like.
In order to produce a multilayer printed wiring board using the composite dielectric material of the present invention, it can be produced by a method known in the art (for example, refer to japanese patent application laid-open nos. 2003-192768, 2005-29700, 2002-226816, 2003-327827, etc.). The following examples are given by way of illustration of the case where a thermosetting resin is used as a polymer material of the composite dielectric material.
The composite dielectric material of the present invention is formed into the above-mentioned dielectric film, and the circuit board is pressed and heated with the resin surface of the dielectric film or laminated by using a vacuum laminator. After the lamination, a metal foil is further laminated on the resin layer exposed by peeling the substrate from the film, and the resin is cured by heating.
When the composite dielectric material of the present invention is formed into a prepreg, lamination to a circuit board can be performed by vacuum pressurization. Specifically, it is desirable to bring one surface of the prepreg into contact with the circuit board, place a metal foil on the other surface, and then apply pressure.
The composite dielectric material of the present invention can be used as a varnish, and can be applied to a circuit board by screen printing, curtain coating, roll coating, spray coating, or the like, and dried to form an intermediate insulating layer of a multilayer printed wiring board.
In the present invention, in the case of a printed wiring board having an insulating layer as the outermost layer, a through hole (via) and a via hole (via) portion are bored by a drill or a laser, and the surface of the insulating layer is roughened to form fine irregularities. The roughening method of the insulating layer can be performed according to specifications such as a method of immersing the substrate on which the insulating resin layer is formed in a solution of an oxidizing agent or the like, a method of spraying a solution of an oxidizing agent or the like, and the like. Specific examples of the roughening agent include dichromate, permanganate, ozone, an oxidizing agent such as hydrogen peroxide/sulfuric acid or nitric acid, an organic solvent such as N-methyl-2-pyrrolidone, N-dimethylformamide or methoxypropanol, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, an acidic aqueous solution such as sulfuric acid or hydrochloric acid, and various plasma treatments. In addition, these processes may be used in combination. As described above, the conductor layer is formed on the roughened insulating layer of the printed wiring board by dry plating such as vapor deposition, sputtering, or ion plating, or wet plating such as electroless plating or electrolytic plating. In this case, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed by electroless plating alone. After the conductor layer is formed in this manner, the annealing treatment is performed to cure the thermosetting resin, whereby the peel strength of the conductor layer can be further improved. In this way, a conductor layer can be formed on the outermost layer.
The metal foil having the intermediate insulating layer formed thereon can be multilayered by lamination by vacuum pressure. The metal foil having the intermediate insulating layer formed thereon can be laminated on a printed wiring board having an inner layer circuit formed thereon by vacuum pressure to form a printed wiring board having a conductor layer as the outermost layer. The prepreg using the composite dielectric material of the present invention can be laminated together with a metal foil on a printed wiring board on which an inner layer circuit is formed by vacuum pressure, thereby forming a printed wiring board having a conductor layer as the outermost layer. In the conformal method, a predetermined through hole and a predetermined via hole are drilled with a drill or a laser beam, and the through hole and the via hole are subjected to desmearing treatment to form fine irregularities. Next, wet plating such as electroless plating and electrolytic plating is performed to obtain conduction between layers.
Further, these steps are repeated several times as necessary, and after the formation of the circuit of the outermost layer is completed, the solder resist is patterned by pattern printing and thermosetting by screen printing, or full-surface printing and thermosetting by curtain coating, roll coating and spray coating, to obtain a desired multilayer printed wiring board.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
< preparation of barium titanate >
7200g of pure water was added to 1300g of barium chloride dihydrate and 1300g of oxalic acid dihydrate, and the mixture was stirred at 55 ℃ for 0.5 hour, and the resulting suspension was used as solution A. In addition, will be oriented to TiO22560g of titanium tetrachloride aqueous solution in terms of 15.3 mass% was diluted with 5600g of pure water to obtain solution B.
Then, the solution B was added to the solution A with stirring at a reaction temperature of 55 ℃ over 30 minutes, and after the addition, the mixture was aged for 0.5 hours with stirring. After the completion of the aging, barium titanyl oxalate was recovered by filtration.
Subsequently, the recovered barium titanyl oxalate was repulped with pure water, and was left to stand and dry at 80 ℃ for 24 hours to obtain a powder of barium titanyl oxalate.
500g of the obtained barium titanyl oxalate powder was put in an alumina crucible, and after presintered at 900 ℃ for 10 hours, it was pulverized by a jet mill, and further presintered at 900 ℃ for 9 hours, to obtain barium titanate (BET specific surface area: 9 m)2(iv)/g, average particle diameter: 0.5 μm).
[ examples 1 to 3]
200g of the barium titanate obtained above was sprayed with a silane coupling agent of the type and amount shown in Table 1 to obtain a mixture of barium titanate and silane coupling agent, and the mixture was fed to a jet mill (STJ 200, SEISHINE corporation) and treated under a grinding pressure of 0.06MPa or more to produce modified barium titanate.
[ comparative example 1]
The obtained barium titanate was supplied to a jet mill without spraying a silane coupling agent, and was treated under a polishing pressure of not less than 0.06MPa to produce a pulverized barium titanate.
[ comparative examples 2 to 4]
Modified barium titanate was produced in the same manner as in examples 1 to 3, except that the type and amount of the surface treatment agent shown in table 1 were changed.
[ Table 1]
TABLE 1
< evaluation >
(degree of aggregation)
The barium titanate of comparative example 1, which was not surface-treated with a silane coupling agent, was measured for average particle size by a laser diffraction scattering method using water as a dispersion medium (D50). The average particle diameter at this time was Dw. Next, the modified barium titanates of examples 1 to 3 and comparative examples 2 to 4 and the barium titanate of comparative example 1 were measured for the average particle diameter by a laser diffraction scattering method using methyl ethyl ketone as a dispersion medium (D50). The average particle diameter at this time was Dos.
The results are shown in table 2, the measurement of the particle size distribution in the organic solvent of the modified barium titanate particles obtained in example 1 is shown in fig. 1, the measurement of the particle size distribution in the organic solvent of the barium titanate particles obtained in comparative example 1 is shown in fig. 2, the measurement of the particle size distribution in water of the barium titanate particles obtained in comparative example 1 is shown in fig. 3, and a laser diffraction particle size distribution measuring apparatus (MT 3300EX, manufactured by microtrac be L) is used for the measurement of the average particle size.
(dissolution test)
2g of the samples obtained in examples 1 to 3 and comparative examples 1 to 4 and 50g of ion-exchanged water were precisely weighed and stirred for 1 hour, 20g of the filtrate obtained by filtering the supernatant with a 0.2 μm pore size syringe filter (syringe filter) was added with 1m L concentrated hydrochloric acid, and the sample solution having a volume of 50m L was quantified by ICP-AES (Agilent 5100, manufactured by Agilent Co.) to evaluate the elution of Ba into water, and the results are shown in Table 2.
(moisture absorption test)
The moisture absorption contents of the samples obtained in examples 1 to 3 and comparative examples 1 to 4 were determined. The results are shown in Table 2.
[ Table 2]
TABLE 2
From the results shown in table 2, the barium titanate of comparative example 1 and the modified barium titanate using the titanium coupling agent of comparative example 2 have a high degree of aggregation in an organic solvent. Further, the modified barium titanate of comparative examples 3 and 4 had a large amount of Ba elution and moisture absorption. On the other hand, it is found that the modified barium titanate obtained in examples 1 to 3 has a low degree of aggregation, suppresses elution of Ba, has a small moisture absorption amount, and is stabilized.
< preparation of strontium titanate >
7200g of pure water was added to 1300g of strontium chloride dihydrate and 1300g of oxalic acid dihydrate, and the mixture was stirred at 55 ℃ for 0.5 hour to obtain a suspension as solution A. In addition, will be oriented to TiO22560g of titanium tetrachloride aqueous solution in terms of 15.3 mass% was diluted with 5600g of pure water to obtain solution B.
Then, the solution B was added to the solution A with stirring at a reaction temperature of 55 ℃ over 30 minutes, and after the addition, the mixture was aged for 0.5 hours with stirring. After the completion of the aging, strontium titanyl oxalate was recovered by filtration.
Subsequently, the recovered strontium titanyl oxalate was repulped with pure water, and was left to stand and dry at 80 ℃ for 24 hours to obtain strontium titanyl oxalate powder.
500g of the obtained strontium titanyl oxalate powder was put into an alumina crucible, presintered at 900 ℃ for 10 hours, then pulverized by a jet mill, and further subjected to pulverizationPrefiring at 900 deg.C for 9 hr, so as to obtain strontium titanate (BET specific surface area: 11 m)2(iv)/g, average particle diameter: 0.4 μm).
[ examples 4 to 6]
200g of the strontium titanate obtained above was sprayed with a silane coupling agent of the kind and amount shown in Table 3 to obtain a mixture of strontium titanate and the silane coupling agent, and the mixture was fed to a jet mill (STJ 200, SEISHINE corporation, Ltd.) and treated under a grinding pressure of 0.06MPa or more to produce modified strontium titanate.
[ comparative example 5]
The obtained strontium titanate is supplied to a jet mill without spraying a silane coupling agent, and is treated under a polishing pressure of not less than 0.06MPa to produce pulverized strontium titanate.
[ comparative examples 6 to 8 ]
Modified strontium titanate was produced in the same manner as in examples 4 to 6, except that the kind and amount of the surface treatment agent shown in Table 3 were changed.
[ Table 3]
TABLE 3
< evaluation >
(degree of aggregation)
The degrees of aggregation of the samples obtained in examples 4 to 6 and comparative examples 5 to 8 were determined in the same manner as in examples 1 to 3 and comparative examples 1 to 4. The results are shown in Table 4.
(dissolution test)
The Sr elution into water of the samples obtained in examples 4 to 6 and comparative examples 5 to 8 was evaluated in the same manner as in examples 1 to 3 and comparative examples 1 to 4. The results are shown in Table 4.
(moisture absorption test)
The moisture content of the samples obtained in examples 4 to 6 and comparative examples 5 to 8 was determined in the same manner as in examples 1 to 3 and comparative examples 1 to 4. The results are shown in Table 4.
[ Table 4]
TABLE 4
From the results shown in Table 4, strontium titanate of comparative example 5 and modified strontium titanate of comparative examples 6 to 8 had high aggregation degree in organic solvents, and the amount of Sr eluted and the amount of hygroscopic moisture were large. On the other hand, it is found that the modified strontium titanates obtained in examples 4 to 6 have a low degree of aggregation, inhibit the elution of Sr, and have a small moisture content in moisture absorption, thereby forming stabilized particles.
< preparation of Potassium sodium niobate >
4688g of niobium pentoxide, 958g of sodium carbonate and 1183g of potassium carbonate were dry-mixed in a Henschel mixer to obtain a raw material mixture.
The raw material mixture was preburnt at 650 ℃ for 7 hours, then pulverized by a jet mill, and preburnt at 900 ℃ for 10 hours, thereby obtaining potassium sodium niobate (BET specific surface area: 3 m)2(iv)/g, average particle diameter: 0.9 μm).
[ example 7 ]
200g of the potassium sodium niobate thus obtained was sprayed with a silane coupling agent of the kind and amount shown in Table 5 to obtain a mixture of potassium sodium niobate and the silane coupling agent, and the mixture was fed to a jet mill (STJ 200, SEISHINE corporation) and treated under a grinding pressure of 0.06MPa or more to produce a modified potassium sodium niobate.
[ comparative example 9 ]
The obtained potassium sodium niobate is supplied to a jet mill without spraying a silane coupling agent thereto, and is treated under a polishing pressure of not less than 0.06MPa to produce pulverized potassium sodium niobate.
[ Table 5]
TABLE 5
| Kinds of surface treating agents | Amount of spray (g) | |
| Example 7 | Decyltrimethoxysilane (KBM-3103, shin-Etsu Silicone Co., Ltd.) | 2.0 |
| Comparative example 9 | Is free of | - |
< evaluation >
(degree of aggregation)
The degrees of aggregation of the samples obtained in examples 7 and comparative examples 9 were determined in the same manner as in examples 1 to 3 and comparative examples 1 to 4. The results are shown in Table 6.
(dissolution test)
The Sr elution into water of the samples obtained in examples 7 and comparative examples 9 was evaluated in the same manner as in examples 1 to 3 and comparative examples 1 to 4. The results are shown in Table 6.
(moisture absorption test)
The moisture content of the samples obtained in examples 7 and comparative examples 9 was determined in the same manner as in examples 1 to 3 and comparative examples 1 to 4. The results are shown in Table 6.
[ Table 6]
TABLE 6
From the results in table 6, the potassium-sodium niobate of comparative example 9 has a high degree of aggregation in an organic solvent, and has a large amount of elution of Na and K and a large amount of moisture in the moisture absorption. On the other hand, it is found that the modified potassium sodium niobate obtained in example 7 has a low degree of aggregation, is inhibited from elution of Na and K, has a small moisture content, and is stabilized.
In addition, the international application claims priority based on japanese patent application No. 2017-243790, which was applied on 12/20/2017, and the entire contents of the japanese patent application are incorporated in the international application.
Claims (10)
1. A modified perovskite-type composite oxide characterized by:
the surface of perovskite-type composite oxide particles is coated with a silane coupling agent represented by the following general formula (1),
(XY)aSi(OZ)4-a(1)
in the general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth) acrylic group, an isocyanate group or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, Z is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group or an alkoxyalkyl group having 2 to 4 carbon atoms, and a is 1 or 2.
2. The modified perovskite-type composite oxide according to claim 1, wherein:
when the average particle diameter D50 of the modified perovskite-type composite oxide measured by a laser diffraction scattering method using an organic solvent as a dispersion medium is Dos and the average particle diameter D50 of the unmodified perovskite-type composite oxide measured by a laser diffraction scattering method using water as a dispersion medium is Dw, the degree of aggregation represented by Dos/Dw is 1.4 or less.
3. The modified perovskite-type composite oxide according to claim 1 or 2, wherein: the moisture content of the moisture absorption is 0.3 mass% or less.
4. The modified perovskite-type composite oxide according to any one of claims 1 to 3, wherein:
the perovskite type composite oxide is barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, potassium sodium lithium niobate, potassium bismuth titanate, sodium bismuth titanate, bismuth ferrite, potassium tantalate or a composite solid solution thereof.
5. A method for producing a modified perovskite-type composite oxide, characterized by comprising:
mixing a perovskite-type composite oxide with a silane coupling agent represented by the following general formula (1), feeding the mixture to a pneumatic pulverizer, pulverizing the perovskite-type composite oxide, coating the surface of perovskite-type composite oxide particles with the silane coupling agent,
(XY)aSi(OZ)4-a(1)
in the general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth) acrylic group, an isocyanate group or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, Z is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group or an alkoxyalkyl group having 2 to 4 carbon atoms, and a is 1 or 2.
6. The method for producing a modified perovskite-type composite oxide according to claim 5, wherein:
the mass ratio of the perovskite-type composite oxide to the silane coupling agent when mixed is 99.5: 0.5 to 95: 5.
7. The method for producing a modified perovskite-type composite oxide according to claim 5 or 6, wherein:
the airflow type pulverizer is a jet mill.
8. The method for producing a modified perovskite-type composite oxide according to any one of claims 5 to 7, wherein:
the pulverization and the surface treatment by the air flow pulverizer are performed under a grinding pressure of 0.03MPa or more.
9. The method for producing a modified perovskite-type composite oxide according to any one of claims 5 to 8, wherein:
the perovskite type composite oxide is barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, potassium sodium lithium niobate, potassium bismuth titanate, sodium bismuth titanate, bismuth ferrite, potassium tantalate or a composite solid solution thereof.
10. A composite dielectric material, characterized by:
a modified perovskite-type composite oxide according to any one of claims 1 to 4 and a polymer material.
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| JP2017-243790 | 2017-12-20 | ||
| JP2017243790 | 2017-12-20 | ||
| PCT/JP2018/042309 WO2019123916A1 (en) | 2017-12-20 | 2018-11-15 | Modified perovskite complex oxide, method for producing same and composite dielectric material |
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| CN113270271A (en) * | 2021-06-02 | 2021-08-17 | 广东工业大学 | Ferroelectric film capacitor and preparation method thereof |
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