KR20200100124A - Modified Perovskite Composite Oxide, Manufacturing Method thereof, and Composite Dielectric Material - Google Patents

Abstract

A modified perovskite composite oxide in which the surface of perovskite composite oxide particles is coated with a silane coupling agent represented by the following general formula (1).
(XY) _a Si(OZ) _4-a (1)
(In general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acryl group, an isocyanate group, or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, and 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.)

Description

Modified Perovskite Composite Oxide, Manufacturing Method thereof, and Composite Dielectric Material

The present invention relates to a modified perovskite-type composite oxide useful as an inorganic filler for a composite dielectric or a composite piezoelectric body, a method for producing the same, and a composite dielectric material containing a modified perovskite-type composite oxide.

BACKGROUND ART [0002] Conventionally, as a passive device requiring high performance in advanced electronic control in the electronics industry, ceramic sintered bodies obtained by molding ceramic powder and then firing it have been widely used. The processing of electronic circuits and mounting of components are complex, yet are receiving many demands such as reduction in cost, space saving, high speed, and high reliability, and continues to evolve even now. Under this background, ceramic sintered bodies are subject to many restrictions due to molding methods such as dimensions, shapes, and mounting. Further, since the sintered body is highly hard and brittle, it is difficult to freely process it, and it is extremely difficult to obtain an arbitrary shape or a complicated shape.

For this reason, composite dielectric materials in which inorganic fillers collectively referred to as dielectrics in a broad sense such as ferroelectrics, pyroelectrics, and piezoelectrics are dispersed in a resin, are excellent in processability, and have various functions such as high dielectric properties, low loss properties, pyroelectric properties, and piezoelectric properties. It is attracting attention as a new material that can be provided.

As the inorganic filler used here, for example, a perovskite type composite oxide is known (see, for example, Patent Document 1). However, the perovskite-type composite oxide has a problem that the specific surface area changes with time and decreases the dielectric properties, and when it comes into contact with water, A-site metals such as Ba, Ca, Sr, and Mg in the structure are eluted. As a result, there is a problem that the interface between the resin and the inorganic filler is peeled off, or insulation deterioration occurs due to ion migration.

On the other hand, as described in Patent Documents 2 to 4, it is known to surface-treat an inorganic filler such as barium titanate with a coupling agent for the purpose of improving dispersibility in a resin.

In Patent Documents 5 and 6, it is described that a metal oxide such as barium titanate is subjected to a surface treatment with a silane coupling agent in order to improve the miscibility with a resin.

International Publication No. 2005/093763 Japanese Patent Publication No. 2003-49092 Japanese Patent Publication No. 2005-15652 Japanese Patent Application Laid-Open No. Hei 7-240117 Japanese Patent Publication No. 2007-308345 Japanese Patent Publication No. 2017-19938

However, as a result of investigation by the present inventors, even if the surface of the perovskite composite oxide particles is simply treated with a coupling agent, the change in specific surface area over time and the elution of the A-site metal such as Ba cannot be sufficiently reduced. It was found that there was room for improvement in the mixability. Homogeneous filling properties for resins and affinity with resins are indispensable for homodispersity in organic solvents, and even if the perovskite-type complex oxide is untreated or surface-treated with a conventional coupling agent, it is sufficiently dispersed in an organic solvent. It was difficult to obtain.

Accordingly, an object of the present invention is to provide a perovskite composite oxide having excellent filling properties and dispersibility in a resin and a method for producing the same in order to solve the above problems.

The present inventors have conducted extensive research in view of the above circumstances. As a result, the perovskite-type composite oxide coated with a specific silane coupling agent has excellent dispersibility in an organic solvent, and the filling property and dispersibility in the resin. This excellent thing was discovered, and the present invention was completed.

That is, the present invention is a modified perovskite composite oxide characterized in that the surface of the perovskite composite oxide particles is coated with a silane coupling agent represented by the following general formula (1).

(XY) _a Si(OZ) _4-a (1)

(In general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acryl group, an isocyanate group, or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, and 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.)

Further, in the present invention, after mixing the perovskite-type composite oxide with the silane coupling agent represented by the general formula (1), the mixture is supplied to an air flow type mill to pulverize the perovskite-type composite oxide. A method for producing a modified perovskite-type composite oxide, characterized in that the surface of the skyt-type composite oxide particle is coated with the silane coupling agent.

According to the present invention, it is possible to provide a modified perovskite composite oxide having excellent filling properties and dispersibility in a resin, and a method for producing the same.

1 is a result of measuring the particle size distribution of modified barium titanate particles obtained in Example 1 in an organic solvent.
2 is a result of measurement of particle size distribution of barium titanate particles obtained in Comparative Example 1 in an organic solvent.
3 is a measurement result of particle size distribution in water of barium titanate particles obtained in Comparative Example 1.

<Modified perovskite type composite oxide>

The modified perovskite-type composite oxide of the present invention is obtained by coating the surface of perovskite-type composite oxide particles with a silane coupling agent represented by the following general formula (1).

(XY) _a Si(OZ) _4-a (1)

(In general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acryl group, an isocyanate group, or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, and 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 barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, sodium potassium niobate, sodium potassium niobate lithium, titanium Potassium bismuth acid, sodium bismuth titanate, bismuth iron acid, potassium tantalate, and the complex solid solution of these include potassium tantalate niobate, potassium niobate sodium tantalate, and the like. These perovskite type composite oxides may be used singly or in combination of two or more.

The production history of such a perovskite composite oxide is not particularly limited, and for example, those obtained by known methods such as a coprecipitation method, a hydrolysis method, a hydrothermal synthesis method and the like, a sol-gel method, and a solid phase method are used. The physical properties of these perovskite composite oxides are not particularly limited, but the BET specific surface area is preferably 0.2 m ² /g to 20 m ² /g, more preferably 0.3 m ² /g to 15 m ² /g. This is preferable from the viewpoint of handling in the pulverizing step. In addition, the average particle diameter of the perovskite composite oxide is preferably 0.1 µm to 10 µm, more preferably 0.15 µm to 5 µm, and handling in the pulverizing step is preferable from the viewpoint of handling. This average particle diameter is a median diameter (D50) measured using water as a dispersion medium by a laser diffraction scattering method.

In addition, the particle shape of the perovskite-type composite oxide to be modified is not particularly limited, and may be any of a spherical shape, a granular shape, a plate shape, a scale shape, a whisker shape, a rod shape, a filament shape, and the like.

In General Formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acryl group, an isocyanate group, or a mercapto group. Among these, it is preferably a hydrogen atom from the viewpoint of imparting dispersibility to a general organic solvent.

Examples of the linear alkylene group having 5 or more carbon atoms represented by Y in the general formula (1) include n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, and n- Decylene group, n-undecylene group, n-dodecylene group, n-tridecylene group, n-tetradecylene group, n-pentadecylene group, n-hexadecylene group, n-heptadecylene group , n-octadecylene group, n-nonadecylene group, etc. are mentioned. From the viewpoint of availability, it is preferable that the number of carbon atoms in the linear alkylene group is 5 or more and 20 or less.

Examples of the alkyl group having 1 to 3 carbon atoms represented by Z in the general formula (1) include a methyl group, an ethyl group, and a propyl group. In addition, examples of the alkoxyalkyl group having 2 to 4 carbon atoms represented by Z in the general formula (1) include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group.

As a specific example of the silane coupling agent represented by general formula (1), hexyltrimethoxysilane (X=hydrogen, Y=n-hexylene group, Z=methyl group, a=1), heptyltrimethoxysilane (X= Hydrogen, Y=n-heptylene group, Z=methyl group, a=1), octyltriethoxysilane (X=hydrogen, Y=n-octylene group, Z=ethyl group, a=1), nonyltrimethoxysilane ( X=hydrogen, Y=n-nonylene group, Z=methyl group, a=1), decyltrimethoxysilane (X=hydrogen, Y=n-decylene group, Z=methyl group, a=1), undecyltri Methoxysilane (X=hydrogen, Y=n-undecylene group, Z=methyl group, a=1), dodecyltrimethoxysilane (X=hydrogen, Y=n-dodecylene group, Z=methyl group, a= 1), tridecyltrimethoxysilane (X=hydrogen, Y=n-tridecylene group, Z=methyl group, a=1), tetradecyltrimethoxysilane (X=hydrogen, Y=n-tetradecylene Group, Z=methyl group, a=1), pentadecyltrimethoxysilane (X=hydrogen, Y=n-pentadecylene group, Z=methyl group, a=1), etc. are mentioned. Among these, hexyltrimethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of imparting dispersibility to a general organic solvent.

Average of the modified perovskite composite oxide of the present invention (perovskite composite oxide coated with a silane coupling agent represented by the general formula (1)) measured by using an organic solvent as a dispersion medium by laser diffraction scattering method The particle diameter (D50) is called Dos, and the average particle diameter (D50) of the unmodified perovskite composite oxide (perovskite composite oxide before modification) measured using water as a dispersion medium by laser diffraction scattering method When is Dw, the degree of cohesion expressed by Dos/Dw is preferably 1.4 or less, and more preferably 1.2 or less. If the degree of aggregation is 1.4 or less, it means that it can be handled in a dispersed state even in an organic solvent, similarly to the perovskite-type composite oxide having relatively good wettability with respect to water. Although it does not specifically limit as an organic solvent used here, Methyl ethyl ketone, acetone, n-hexane, methanol, ethanol, toluene, cyclopentanone, etc. are mentioned.

In addition, the modified perovskite composite oxide of the present invention preferably has a moisture absorption content of 0.3% by mass or less, and more preferably 0.25% by mass or less. When the moisture absorption moisture content is 0.3% by mass or less, the degree to which the surface of the perovskite composite oxide as a base material changes to a hydroxide or a carbonate compound by moisture is low, and a change in particle shape and a decrease in electrical properties can be prevented. In addition, in this specification, the moisture absorption moisture content of a modified perovskite type composite oxide is calculated|required by the following method.

First, a modified perovskite-type composite oxide sample immediately after production is accurately weighed (A), and the dried product obtained by heating this sample in a shelf-stage dryer at 105° C. for 2 hours is accurately weighed (B). Separately from this, a modified perovskite-type composite oxide sample immediately after production is accurately weighed (a), and the sample is allowed to stand for 180 minutes in an environment of 40°C and 90% humidity to absorb moisture, and thus a moisture absorption sample obtained is accurately measured (c). The dried product obtained by heating this moisture absorption sample in a drying machine at 105° C. for 2 hours is accurately weighed (b). The amount of adhered moisture is determined by the following equation, and it is taken as the amount of moisture absorbed into the sample (mass%).

Moisture absorption (% by mass) = (((c-b)/a)×100)-(((A-B)/A)×100)

The modified perovskite-type composite oxide of the present invention is obtained by mixing the perovskite-type composite oxide to be modified with the silane coupling agent represented by the general formula (1), and then supplying the mixture to an air flow type mill. , It can be produced by pulverizing the perovskite-type composite oxide and coating the surface of the perovskite-type composite oxide particles with a silane coupling agent. By supplying a mixture of the perovskite-type composite oxide and the silane coupling agent represented by the general formula (1) to an airflow-type grinder, a new surface of the perovskite-type composite oxide exposed in the process of being pulverized is obtained from the general formula ( Since it can be immediately coated with the silane coupling agent represented by 1), the chance of exposure to the surrounding environment and contact with moisture can be reduced, and elution of the A-site metal and changes in the specific surface area over time can be suppressed.

The mixing method of the perovskite composite oxide and the silane coupling agent is not particularly limited, but a method of spraying a silane coupling agent onto the perovskite composite oxide, and a solid silane coupling agent with the perovskite composite oxide and dry method A method of mixing, a method of adding a liquid silane coupling agent to the perovskite-type composite oxide dispersed in an organic solvent, followed by filtration and drying to obtain a mixture, and the like. The silane coupling agent may be used as an undiluted solution, or dissolved in a suitable solvent (alcohols, ketones, ethers, etc.) may be used. When mixing the perovskite composite oxide and the silane coupling agent, the mass ratio of the perovskite composite oxide and the silane coupling agent is preferably 99.5:0.5 to 95:5, and 99:1 to 96:4. It is more preferable. When the mass ratio of the perovskite-type composite oxide and the silane coupling agent is 99.5:0.5 to 95:5, at least one layer of a silane coupling agent film can be formed on the surface of the perovskite-type composite oxide particles. However, even if a large amount of the silane coupling agent is added, the obtained effect is not amplified, which is economically disadvantageous.

Examples of the air-flow type pulverizer include a jet mill, a stream mill, and a fluid bed pulverizer. Among these, a jet mill is preferred from the viewpoint of less contamination due to a structure in which no blades or media are placed in the grinding chamber.

Although it does not specifically limit as a grinding|pulverization condition by an air flow type grinder, It is a grinding pressure of preferably 0.03 MPa or more, more preferably 0.05 MPa to 0.7 MPa. In addition, although the powder input speed varies depending on the size of the air flow type mill, it is preferably 4 to 40 kg/hr. By performing under this pulverization condition, the silane coupling agent represented by the general formula (1) can be sufficiently and efficiently coated on the surface of the newly exposed perovskite composite oxide.

Since the modified perovskite-type composite oxide of the present invention obtained in this way is excellent in filling and dispersing properties in the resin, the composite dielectric material described below is excellent in high dielectric properties, low loss properties, pyroelectric properties, piezoelectric properties, etc. It becomes possible to manufacture. In addition, the modified perovskite type composite oxide of the present invention can be a ferroelectric, a pyroelectric, and a piezoelectric material, but in a broad sense, it is generically referred to as a dielectric including a phase dielectric.

<Composite dielectric material>

The composite dielectric material of the present invention contains a polymer material and the modified perovskite composite oxide as an inorganic filler. The composite dielectric material of the present invention contains preferably 60% by mass or more, more preferably 70% by mass to 90% by mass of the modified perovskite composite oxide in the polymer material described later, and preferably 15 or more, More preferably, it is preferably a material having a relative dielectric constant of 20 or more.

As a polymer material that can be used in the present invention, a thermosetting resin, a thermoplastic resin, or a photosensitive resin can be mentioned.

Examples of thermosetting resins include epoxy resins, phenolic resins, polyimide resins, melamine resins, cyanate resins, bismaleimides, bismaleimides and diamine addition polymerization products, polyfunctional cyanate ester resins, double bond addition Known things, such as a polyphenylene oxide resin, an unsaturated polyester resin, a polyvinyl benzyl ether resin, a polybutadiene resin, and a fumarate resin, are mentioned. These thermosetting resins may be used singly or in combination of two or more. Among these thermosetting resins, epoxy resins and polyvinyl benzyl ether resins are preferred from the balance of heat resistance, processability, and cost.

The epoxy resin used in the present invention is a monomer, oligomer, and general polymer having at least two epoxy groups in one molecule. For example, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin including phenol, cresol, and Phenols such as silenol, resorcin, catechol, bisphenol A and bisphenol F, and/or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicyl Diglycidyl such as bisphenol A, bisphenol B, bisphenol F, bisphenol S, alkyl substituted or unsubstituted biphenol, etc., obtained by epoxidizing novolac resin obtained by condensing or co-condensing aldehydes such as aldehydes under an acidic catalyst Epoxyized product of ether, phenols and dicyclopentadiene or terpene adducts or polyadditions, glycidyl ester type epoxy resin obtained by reaction of epichlorohydrin with polybasic acids such as phthalic acid and dimer acid, dia Glycidylamine-type epoxy resin obtained by reaction of epichlorohydrin with polyamine such as minodiphenylmethane and isocyanuric acid, linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peracids such as peracetic acid, and alicyclic epoxy Resin, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the epoxy resin curing agent, all known ones can be used, but in particular, C ₂ to C ₂₀ linear aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine and hexamethylenediamine, metaphenylenediamine, and paraphenyl Rendiamine, paraxylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone , 4,4'-diaminodicyclohexane, bis(4-aminophenyl)phenylmethane, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis(4- Amines such as aminophenyl)cyclohexane, dicyanodiamide, phenol novolac resin, cresol novolac resin, tert-butylphenol novolak resin, novolac-type phenol resin such as nonylphenol novolac resin, resol-type phenol resin, A phenol compound in which a hydrogen atom bonded to a benzene ring, naphthalene ring, or other aromatic ring is substituted with a hydroxyl group, such as polyoxy styrene such as polyparaoxy styrene, a phenol aralkyl resin, or a naphthol aralkyl resin, and a carbonyl compound. A phenol resin obtained by co-condensation, an acid anhydride, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The blending amount of the epoxy resin curing agent is preferably 0.1 to 10, more preferably 0.7 to 1.3 in an equivalent ratio with respect to the epoxy resin.

Further, in the present invention, a known curing accelerator may be used for the purpose of accelerating 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, 2-methylimidazole, 2 -Imidazole compounds such as ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole, organic phosphine compounds such as triphenylphosphine and tributylphosphine, phosphine A phonium salt, an ammonium salt, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The polyvinyl benzyl ether resin used in the present invention is 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 General Formula (2), R ₁ represents a methyl group or an ethyl group. R ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group represented by R ₂ is an alkyl group, an aralkyl group, an aryl group and the like which may have a substituent. As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned, for example. As an aralkyl group, a benzyl group etc. are mentioned, for example. As an aryl group, a phenyl group etc. are mentioned, for example. R ₃ represents a hydrogen atom or a vinylbenzyl group. In addition, the hydrogen atom of R ₃ is derived from the starting compound when synthesizing the compound of general formula (2), and if the molar ratio of the hydrogen atom and the vinylbenzyl group is 60:40 to 0:100, the curing reaction is sufficiently advanced. In addition, in the composite dielectric material of the present invention, it is preferable from the viewpoint of obtaining sufficient dielectric properties. n represents the integer of 2-4.

The polyvinyl benzyl ether compound may be used by polymerizing only it as a resin material, or may be used by copolymerizing with another monomer. Examples of copolymerizable monomers include styrene, vinyl toluene, divinylbenzene, divinylbenzyl ether, allylphenol, allyloxybenzene, diallylphthalate, acrylic acid ester, methacrylic acid ester, vinylpyrrolidone, and modified products thereof. I can. The blending ratio of these monomers is 2% by mass to 50% by mass based on the polyvinylbenzyl ether compound.

The polymerization and curing of the polyvinyl benzyl ether compound can be performed by a known method. Curing may be performed in the presence or absence of a curing agent. As the curing agent, known radical polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl perbenzoate can be used, for example. The amount used is 0 to 10 parts by mass based on 100 parts by mass of the polyvinyl benzyl ether compound. The curing temperature varies depending on the presence or absence of a curing agent and the type of curing agent, but in order to sufficiently cure, it is preferably 20°C to 250°C, more preferably 50°C to 250°C.

Further, in order to adjust the curing, hydroquinone, benzoquinone, copper salt, or the like may be blended.

Examples of the thermoplastic resin include known ones such as (meth)acrylic resin, hydroxystyrene resin, novolac resin, polyester resin, polyimide resin, nylon resin, and polyetherimide resin.

As a photosensitive resin, well-known things, such as a photopolymerizable resin and a photocrosslinkable resin, are mentioned, for example.

The photopolymerizable resin used in the present invention includes, for example, an acrylic copolymer (photosensitive oligomer) having an ethylenically unsaturated group, a photopolymerizable compound (photosensitive monomer), and a photopolymerization initiator, and an epoxy resin and a photocationic polymerization initiator. And things to do. As photosensitive oligomers, those obtained by adding acrylic acid to an epoxy resin, further reacting it with an acid anhydride, or reacting (meth)acrylic acid to a copolymer containing a (meth)acrylic monomer having a glycidyl group, and an acid A reaction of an anhydride, a reaction of glycidyl (meth)acrylate with a copolymer containing a (meth)acrylic monomer having a hydroxyl group, further reaction of an acid anhydride therewith, a copolymer containing maleic anhydride The reaction of a (meth)acrylic monomer having a hydroxyl group or a (meth)acrylic monomer having a glycidyl group may be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As a photopolymerizable compound (photosensitive monomer), for example, 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,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, tris( Hydroxyethyl) isocyanurate tri(meth)acrylate, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As a photoinitiator, benzoin and its alkyl ethers, benzophenones, acetophenones, anthraquinones, xanthones, thioxanthones, etc. are mentioned, for example. These may be used individually by 1 type, and may be used in combination of 2 or more types. Further, these photopolymerization initiators can be used in combination with known and commonly used photopolymerization accelerators such as benzoic acid and tertiary amines. As a photocationic polymerization initiator, for example, triphenylsulfonium hexafluoroantimonate, diphenylsulfoniumhexafluoroantimonate, triphenylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium Hexafluorophosphate and iron aromatic compound salts of Bronsted acid (Ciba-Geigi, CG24-061), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the epoxy resin is ring-opened and polymerized by the photocationic polymerization initiator, the photopolymerization is more preferable because the reaction rate is faster than the usual glycidyl ester epoxy resin. An alicyclic epoxy resin and a glycidyl ester type epoxy resin can also be used together. As an alicyclic epoxy resin, for example, vinylcyclohexene diepoxide, alicyclic diepoxycetal, alicyclic diepoxydipate, alicyclic diepoxycarboxylate, Daicel Chemical Co., Ltd. make, EHPE -3150 etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the photocrosslinkable resin include water-soluble polymer dichromate, polycinnamate vinyl (Kodak KPR), cyclized rubber azide (Kodak KTFR), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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 binder, a polymer having more high dielectric properties (for example, Sumitomo Chemical's SDP-E (ε: 15<), Shin-Etsu Chemical's Cyano resin (ε: 18<)) or a highly dielectric liquid (eg, Sumitomo Chemical's SDP-S (ε: 40<)) can also be added.

In the present invention, the polymer materials described above may be used singly or in combination of two or more.

In the composite dielectric material of the present invention, the blending amount of the modified perovskite-type composite oxide is a proportion of the composite oxide with the resin, preferably 60% by mass or more, and more preferably 70% by mass to 90% by mass. . The reason for this is that when it is less than 60% by mass, a sufficient relative dielectric constant tends not to be obtained. On the other hand, when it exceeds 90% by mass, the viscosity increases and the dispersibility tends to deteriorate. This is because there is a risk of not being obtained or not. It is preferable that it is a material having a relative dielectric constant of preferably 15 or more, more preferably 20 or more by the above formulation.

In addition, the composite dielectric material of the present invention may contain other fillers in an added amount within a range that does not impair the effects of the present invention. Examples of other fillers include carbon fine powder such as acetylene black and Ketjen black, graphite fine powder, and silicon carbide.

In addition, the composite dielectric material of the present invention includes a curing agent, a glass powder, a polymer additive, a reactive diluent, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, as long as the effect of the present invention is not impaired. Antioxidants, antistatic agents, inorganic fillers, mold inhibitors, humidifiers, dye solubilizers, buffers, chelating agents, flame retardants, and the like may be added. These additives may be used individually by 1 type, and may be used in combination of 2 or more types.

The composite dielectric material of the present invention can be produced by preparing a composite dielectric paste and performing an organic solvent removal, curing reaction, or polymerization reaction.

The composite dielectric paste contains a resin component, a modified perovskite composite oxide, an additive added as necessary, and an organic solvent.

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. In addition, these resin components may be used individually by 1 type, and may be used in combination of 2 or more types.

Here, the polymerizable compound represents a compound having a polymerizable group, and includes, for example, a precursor polymer, a polymerizable oligomer, and a monomer before complete curing. In addition, a polymer refers to a compound in which the polymerization reaction has been substantially completed.

The organic solvent to be added as needed is not particularly limited as long as it differs depending on the resin component to be used and can dissolve the resin component. For example, N-methylpyrrolidone, dimethylformamide, ether, diethyl Ether, tetrahydrofuran, dioxane, ethyl glycol ether, propylene glycol ether, butyl glycol ether, ketone, acetone, methyl ethyl ketone, methyl isopropyl of a monoalcohol having a straight or branched alkyl group having 1 to 6 carbon atoms 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 or in combination of two or more. Among these, hexane, heptane, cyclohexane, toluene and dixylene are preferable.

In the present invention, the composite dielectric paste is prepared and used to a desired viscosity. The viscosity of the composite dielectric paste is usually 1,000 mPa·s to 1,000,000 mPa·s (25°C), and in consideration of the applicability of the composite dielectric paste, it is preferably 10,000 mPa·s to 600,000 mPa·s (25° C.).

The composite dielectric material of the present invention can be processed and used as a film, a bulk, or a molded article having a predetermined shape, and in particular, can be used as a thin film-shaped high dielectric film.

In order to manufacture a composite dielectric film using the composite dielectric material of the present invention, for example, it may be produced according to a conventionally known method of using a composite dielectric paste, and an example thereof is shown below.

The composite dielectric paste can be applied onto a substrate and then dried to form a film. As the substrate, for example, a plastic film having a peeling treatment on its surface can be used. In the case of coating on a plastic film subjected to a peeling treatment and molding into a film, it is generally preferred to peel the substrate from the film after molding to be used. As a plastic film which can be used as a base material, films, such as a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, a polyester film, a polyimide film, aramid, Kapton, and polymethylpentene, are mentioned. In addition, the thickness of the plastic film used as the substrate is preferably 1 µm to 100 µm, and more preferably 1 µm to 40 µm. Further, as the release treatment performed on the surface of the substrate, a release treatment in which silicone, wax, fluororesin, or the like is applied to the surface is preferably used.

Moreover, you may use a metal foil as a base material, and you may form a dielectric film on the metal foil. In this case, the metal foil used as the base material can be used as the electrode of the capacitor.

The method of applying the composite dielectric paste on the substrate is not particularly limited, and a general application method can be used. For example, it can be applied by a roller method, a spray method, a silk screen method, or the like.

Such a dielectric film can be thermally cured by heating after being embedded in a substrate such as a printed circuit board. In addition, when a photosensitive resin is used, patterning can be performed by selectively exposing.

Further, for example, the composite dielectric material of the present invention may be extrusion-molded by a calender method or the like to form a film.

The dielectric film extruded may be molded so as to be extruded onto the substrate. In addition, when a metal foil is used as a base material, as the metal foil, in addition to a foil made of copper, aluminum, brass, nickel, iron or the like as a material, alloy foils, composite foils and the like thereof can be used. If necessary, the metal foil may be subjected to a treatment such as surface roughening or application of an adhesive.

Further, a dielectric film may be formed between the metal foils. In this case, a dielectric film sandwiched between the metal foils may be formed by applying the composite dielectric paste on the metal foil, placing the metal foil thereon, and drying the composite dielectric paste sandwiched between the metal foils. Further, by extrusion molding so as to be sandwiched between metal foils, a dielectric film provided between metal foils may be formed.

Further, the composite dielectric material of the present invention may be used as a prepreg by making a varnish using the organic solvent described above, impregnating it with a cloth or nonwoven fabric, and drying. The kind of cloth or nonwoven fabric that can be used is not particularly limited, and a known one can be used. Examples of the cloth include glass cloth, aramid cloth, carbon cloth, and stretched porous polytetrafluoroethylene. Moreover, as a nonwoven fabric, an aramid nonwoven fabric, glass paper, etc. are mentioned. The prepreg is laminated on an electronic component such as a circuit board and then cured to introduce an insulating layer into the electronic component.

Since the composite dielectric material of the present invention has a high dielectric constant, it can be suitably used as a dielectric layer of electronic components, particularly electronic components such as printed circuit boards, semiconductor packages, capacitors, high frequency antennas, and inorganic ELs.

In order to manufacture a multilayer printed wiring board using the composite dielectric material of the present invention, it can be manufactured using a method known in the art (for example, Japanese Patent Laid-Open No. 2003-192768, Japanese Patent Laid-Open No. See 2005-29700, Japanese Patent Publication No. 2002-226816, Japanese Patent Application Publication No. 2003-327827, etc.). In addition, an example shown below is an example in the case of using a thermosetting resin as a polymer material of a composite dielectric material.

The composite dielectric material of the present invention is used as the above-described dielectric film, and is laminated by pressing and heating a circuit board on the resin surface of the dielectric film or using a vacuum laminator. After lamination, the base material is peeled from the film, and a metal foil is further laminated on the exposed resin layer to heat cure the resin.

In addition, lamination of the composite dielectric material of the present invention as a prepreg onto a circuit board can be performed by vacuum pressing. Specifically, it is preferable that one surface of the prepreg is brought into contact with a circuit board, and a metal foil is placed on the other surface to perform pressing.

Further, an intermediate insulating layer of a multilayer printed circuit board can be formed by using the composite dielectric material of the present invention as a varnish and applying and drying the circuit board using screen printing, curtain coating, roll coating, spray coating, or the like.

In the present invention, in the case of a printed wiring board having an insulating layer on the outermost layer, through-holes and via-holes are drilled or drilled with a laser, and the surface of the insulating layer is treated with a roughening agent to form fine irregularities. As a roughening method of the insulating layer, it can be carried out according to specifications such as a method of immersing the substrate on which the insulating resin layer is formed in a solution such as an oxidizing agent, or a method of spraying a solution such as an oxidizing agent. Specific examples of the roughening treatment agent include oxidizing agents such as dichromate, permanganate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid, organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and methoxypropanol, and Alkaline aqueous solutions such as caustic soda and caustic potassium, acidic aqueous solutions such as sulfuric acid and hydrochloric acid, or various plasma treatments can be used. In addition, these treatments may be used in combination. As described above, on the printed wiring board in which the insulating layer is harmonized, a conductor layer is then formed by dry plating such as vapor deposition, sputtering, or ion plating, or wet plating such as electroless/electrolytic plating. At this time, a plating resist having a reverse pattern may be formed with the conductor layer, and the conductor layer may be formed only by electroless plating. After the conductor layer is formed in this way, by annealing treatment, the curing of the thermosetting resin proceeds and the peel strength of the conductor layer can be further improved. In this way, a conductor layer can be formed on the outermost layer.

Moreover, the metal foil in which the intermediate insulating layer was formed can be multilayered by laminating by vacuum press. The metal foil having the intermediate insulating layer formed thereon can be laminated by vacuum pressing on a printed wiring board on which an inner circuit is formed, thereby making the outermost layer a printed wiring board of a conductor layer. In addition, the prepreg using the composite dielectric material of the present invention can be laminated with a metal foil on a printed wiring board on which an inner circuit is formed by vacuum pressing, so that the outermost layer can be a printed wiring board of a conductor layer. A predetermined through-hole and a via hole are drilled or drilled with a laser by a conformal method or the like, and the through-hole and the via-hole are desmeared to form fine irregularities. Subsequently, conduction between the layers is achieved by wet plating such as electroless/electrolytic plating.

In addition, if necessary, these processes are repeated several times, and after the formation of the circuit of the outermost layer is completed, the solder resist is applied by pattern printing/thermal curing by the screen printing method, or by curtain coating/roll coating/spray coating. A desired multilayer printed wiring board is obtained by forming a pattern with a laser after full surface printing and heat curing.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited thereto.

<Preparation of barium titanate>

7200 g of pure water was added to 1300 g of barium chloride dihydrate and 1300 g of oxalic acid dihydrate, and the suspension obtained by stirring at a temperature of 55° C. for 0.5 hours was referred to as Solution A. In addition, 5600 g of pure water was added and diluted to 2560 g of 15.3 mass% titanium tetrachloride aqueous solution in terms of TiO ₂ , and this was referred to as Liquid B.

Subsequently, while stirring, the liquid B was added to the liquid A over 30 minutes at a reaction temperature of 55°C, and after the addition, aging for 0.5 hours was performed while continuing stirring. After completion of aging, it was filtered to recover barium titanyl oxalate.

Subsequently, the recovered barium titanyl oxalate was repulped with pure water, and dried at 80°C for 24 hours to obtain a powder of barium titanyl oxalate.

500 g of the obtained barium titanyl oxalate powder was put in an alumina crucible, calcined at 900° C. for 10 hours, pulverized by a jet mill, and calcined at 900° C. for 9 hours, thereby barium titanate (BET specific surface area: 9 m ² / g, average particle diameter: 0.5 µm) was obtained.

[Examples 1 to 3]

With respect to 200 g of barium titanate obtained above, a mixture of barium titanate and a silane coupling agent was obtained by spraying a silane coupling agent of the type and amount shown in Table 1, and the mixture was used in a jet mill (STJ200 manufactured by Seishin Engineering Co., Ltd.). ) And treated under conditions of a grinding pressure ≥ 0.06 MPa to prepare a modified barium titanate.

[Comparative Example 1]

The barium titanate obtained above was supplied to a jet mill without spraying a silane coupling agent, and treated under conditions of a grinding pressure ≥0.06 MPa to prepare 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.

<Evaluation>

(Coagulation degree)

For barium titanate not subjected to the surface treatment with the silane coupling agent of Comparative Example 1, water was used as a dispersion medium, and the average particle diameter (D50) was determined by laser diffraction scattering method. The average particle diameter at this time was referred to as Dw. Next, with respect to the modified barium titanate of Examples 1 to 3 and Comparative Examples 2 to 4, and the barium titanate of Comparative Example 1, the average particle diameter (D50) by laser diffraction scattering method using methyl ethyl ketone as a dispersion medium. Was obtained. The average particle diameter at this time was called Dos.

From the obtained measured value, Dos/Dw was calculated, and the degree of aggregation of particles in an organic solvent was taken. The results are shown in Table 2. In addition, the particle size distribution measurement of the modified barium titanate particles obtained in Example 1 in an organic solvent is shown in FIG. 1, and the particle size distribution measurement results of the barium titanate particles obtained in Comparative Example 1 in an organic solvent are shown in FIG. And Fig. 3 shows the result of measuring the particle size distribution in water of the barium titanate particles obtained in Comparative Example 1. In addition, for the measurement of the average particle diameter, a laser diffraction type particle size distribution measuring device (made by Microtrac Bell, MT3300EX) was used.

(Dissolution test)

2 g of samples obtained in each of Examples 1 to 3 and Comparative Examples 1 to 4 and 50 g of ion-exchanged water were accurately weighed and stirred for 1 hour, and then 1 mL of concentrated hydrochloric acid was added to 20 g of the filtrate filtered through a syringe filter having a 0.2 μm pore diameter. Then, the sample solution determined to be 50 mL was quantified by ICP-AES (Agilent 5100 manufactured by Agilent Corporation), and the elution of Ba into water was evaluated. The results are shown in Table 2.

(Hygroscopicity test)

The moisture absorption amount of the samples obtained in each of Examples 1 to 3 and Comparative Examples 1 to 4 was calculated. The results are shown in Table 2.

From the results of Table 2, in the barium titanate of Comparative Example 1 and the modified barium titanate by the titanium coupling agent of Comparative Example 2, the degree of aggregation in an organic solvent was high. In addition, in the modified barium titanate of Comparative Example 3 and Comparative Example 4, the elution amount and moisture absorption amount of Ba were large. In contrast, in the modified barium titanate obtained in Examples 1 to 3, it can be seen that the degree of aggregation is low, the elution of Ba is suppressed, the moisture absorption amount is small, and the particles are stabilized.

<Preparation of strontium titanate>

7200 g of pure water was added to 1300 g of strontium chloride dihydrate and 1300 g of oxalic acid dihydrate, and a suspension obtained by stirring at a temperature of 55° C. for 0.5 hours was referred to as Solution A. In addition, 5600 g of pure water was added and diluted to 2560 g of 15.3 mass% titanium tetrachloride aqueous solution in terms of TiO ₂ , and this was referred to as Liquid B.

Subsequently, while stirring, the liquid B was added to the liquid A over 30 minutes at a reaction temperature of 55°C, and after the addition, aging for 0.5 hours was performed while continuing stirring. After completion of aging, strontium titanyl oxalate was recovered by filtration.

Subsequently, the recovered strontium titanyl oxalate was repulped with pure water and dried at 80°C for 24 hours to obtain a powder of strontium titanyl oxalate.

500 g of the obtained strontium titanyl oxalate powder was put into an alumina crucible, calcined at 900° C. for 10 hours, pulverized by a jet mill, and calcined at 900° C. for 9 hours, thereby strontium titanate (BET specific surface area: 11 m ² / g, average particle diameter: 0.4 µm) was obtained.

[Examples 4 to 6]

With respect to 200 g of strontium titanate obtained above, a mixture of strontium titanate and a silane coupling agent was obtained by spraying a silane coupling agent of the kind and amount shown in Table 3, and the mixture was used as a jet mill (STJ200, manufactured by Seishin Engineering Co., Ltd. ) And treated under conditions of grinding pressure ≥ 0.06 MPa to prepare modified strontium titanate.

[Comparative Example 5]

The strontium titanate obtained above was supplied to a jet mill without spraying a silane coupling agent, and treated under conditions of a grinding pressure ≥ 0.06 MPa to prepare 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 type and amount of the surface treatment agent shown in Table 3 were changed.

<Evaluation>

(Coagulation degree)

In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the degree of aggregation of the samples obtained in each of Examples 4 to 6 and Comparative Examples 5 to 8 was calculated. The results are shown in Table 4.

(Dissolution test)

In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the elution of Sr into the water of the samples obtained in each of Examples 4 to 6 and Comparative Examples 5 to 8 was evaluated. The results are shown in Table 4.

(Hygroscopicity test)

In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the moisture absorption moisture content of the samples obtained in each of Examples 4 to 6 and Comparative Examples 5 to 8 was calculated. The results are shown in Table 4.

From the results of Table 4, in the strontium titanate of Comparative Example 5 and the modified strontium titanate of Comparative Examples 6 to 8, the degree of aggregation in an organic solvent was high, and the elution amount of Sr and the moisture absorption amount were large. In contrast, in the modified strontium titanate obtained in Examples 4 to 6, it can be seen that the degree of aggregation is low, the elution of Sr is suppressed, the moisture absorption amount is small, and the particles are stabilized.

<Preparation of sodium potassium niobate>

4688 g of niobium pentoxide, 958 g of sodium carbonate, and 1183 g of potassium carbonate were dry mixed with a Henschel mixer to obtain a raw material mixture.

This raw material mixture was calcined at 650°C for 7 hours, then pulverized by a jet mill, and then calcined at 900°C for 10 hours to obtain sodium potassium niobate (BET specific surface area: 3 m ² /g, average particle diameter: 0.9 μm). Got it.

[Example 7]

With respect to 200 g of sodium potassium niobate obtained above, a mixture of sodium potassium niobate and a silane coupling agent was obtained by spraying a silane coupling agent of the type and amount shown in Table 5, and the mixture was used in a jet mill (Seishin Co., Ltd. It was supplied to a teacher's STJ200) and treated under conditions of a grinding pressure ≥0.06 MPa to prepare a modified sodium potassium niobate.

[Comparative Example 9]

The sodium potassium niobate obtained above was supplied to a jet mill without spraying a silane coupling agent, and treated under conditions of a grinding pressure ≥ 0.06 MPa to prepare pulverized sodium potassium niobate.

<Evaluation>

(Coagulation degree)

In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the degree of aggregation of the samples obtained in each of Example 7 and Comparative Example 9 was determined. The results are shown in Table 6.

(Dissolution test)

In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the elution of Sr into the water of the samples obtained in each of Examples 7 and 9 was evaluated. The results are shown in Table 6.

(Hygroscopicity test)

In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the moisture absorption moisture content of the samples obtained in each of Examples 7 and 9 was determined. The results are shown in Table 6.

From the results of Table 6, in the sodium potassium niobate of Comparative Example 9, the degree of aggregation in an organic solvent was high, and the elution amount of Na and K and the moisture absorption amount were large. In contrast, in the modified sodium potassium niobate obtained in Example 7, the degree of aggregation was low, the elution of Na and K was suppressed, and the moisture absorption amount was small, and the particles were stabilized.

In addition, this international application claims the priority based on Japanese Patent Application No. 2017-243790 for which it applied on December 20, 2017, and uses the whole content of this Japanese patent application for this international application.

Claims (10)

A modified perovskite-type composite oxide, characterized in that the surface of the perovskite-type composite oxide particles is coated with a silane coupling agent represented by the following general formula (1).
(XY) _a Si(OZ) _4-a (1)
(In general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acryl group, an isocyanate group or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, and 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 method of claim 1, wherein the average particle diameter (D50) of the modified perovskite composite oxide measured using an organic solvent as a dispersion medium by a laser diffraction and scattering method is referred to as Dos, and water is dispersed by a laser diffraction and scattering method. When the average particle diameter (D50) of the unmodified perovskite-type composite oxide measured using as Dw is Dw, the degree of aggregation expressed in Dos/Dw is 1.4 or less. The perovskite composite oxide according to claim 1 or 2, wherein the moisture absorption moisture content is 0.3% by mass or less. The method according to any one of claims 1 to 3, wherein the perovskite composite oxide is barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, sodium potassium niobate, niobic acid. A modified perovskite-type composite oxide, characterized in that lithium potassium sodium, potassium bismuth titanate, sodium bismuth titanate, bismuth iron acid, potassium tantalate, or a complex solution thereof. Perovskite-type composite oxide particles are mixed with a silane coupling agent represented by the following general formula (1), and then the mixture is supplied to an airflow mill to pulverize the perovskite-type composite oxide while pulverizing the perovskite-type composite oxide particles. A method for producing a modified perovskite composite oxide, characterized in that the surface of the silane coupling agent is coated with the silane coupling agent.
(XY) _a Si(OZ) _4-a (1)
(In general formula (1), X is a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acryl group, an isocyanate group, or a mercapto group, Y is a linear alkylene group having 5 or more carbon atoms, and 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 method for producing a modified perovskite-type composite oxide according to claim 5, wherein a mass ratio of the perovskite-type composite oxide and the silane coupling agent at the time of mixing is 99.5:0.5 to 95:5. The method for producing a modified perovskite-type composite oxide according to claim 5 or 6, wherein the air flow type mill is a jet mill. The method for producing a modified perovskite-type composite oxide according to any one of claims 5 to 7, wherein the pulverization and surface treatment by the air flow type grinder are performed at a grinding pressure of 0.03 MPa or more. The method according to any one of claims 5 to 8, wherein the perovskite composite oxide is barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, sodium potassium niobate, niobic acid. Lithium potassium sodium, potassium bismuth titanate, sodium bismuth titanate, bismuth iron acid, potassium tantalate, or a method for producing a modified perovskite composite oxide, characterized in that it is a complex solution thereof. A composite dielectric material comprising the modified perovskite composite oxide according to any one of claims 1 to 4 and a polymer material.

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