WO2019123916A1

WO2019123916A1 - Modified perovskite complex oxide, method for producing same and composite dielectric material

Info

Publication number: WO2019123916A1
Application number: PCT/JP2018/042309
Authority: WO
Inventors: 淳史 ▲高▼▲崎▼; 田邉　信司
Original assignee: 日本化学工業株式会社
Priority date: 2017-12-20
Filing date: 2018-11-15
Publication date: 2019-06-27
Also published as: CN111511686A; JP7204673B2; JPWO2019123916A1; KR102510234B1; KR20200100124A

Abstract

A modified perovskite complex oxide which is obtained by covering the surface of a perovskite complex oxide particle with a silane coupling agent that is represented by general formula (1). (1): (XY)_aSi(OZ)_4-a (In general formula (1), X represents a hydrogen atom, an epoxy group, an amino group, a vinyl group, a (meth)acrylic group, an isocyanate group or a mercapto group; Y represents a linear alkylene group having 5 or more carbon atoms; Z represents a hydrogen atom, an alkyl group having 1-3 carbon atoms, an acetyl group or an alkoxyalkyl group having 2-4 carbon atoms; and a represents 1 or 2.)

Description

Modified perovskite-type composite oxide, method for producing the same, 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 composite piezoelectric material, a method for producing the same, and a composite dielectric material containing the modified perovskite-type composite oxide.

Heretofore, as a passive device requiring high performance in the advanced electronic control in the electronics industry, a ceramic sintered body obtained by forming a ceramic powder and firing it has been widely used. The The management of electronic circuits and the mounting of parts have continued to evolve in response to many demands such as cost reduction, space saving, speeding up and high reliability while becoming complicated. With such a background, ceramic sintered bodies are subject to many limitations due to forming methods such as dimensions, shapes and mounting. In addition, since the sintered body is high in hardness and brittle, free processing is difficult, and it is extremely difficult to obtain an arbitrary shape or a complicated shape.
For this reason, a composite dielectric material in which an inorganic filler generally referred to as a dielectric in a broad sense, such as a ferroelectric, a pyroelectric or a piezoelectric, is dispersed in a resin is excellent in processability and has high dielectric characteristics and low loss characteristics. It is attracting attention as a new material that can have various functions such as pyroelectric characteristics and piezoelectric characteristics.
As an inorganic filler used here, for example, a perovskite type complex 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 the dielectric characteristics are degraded, and when it comes in contact with water, A site metals such as Ba, Ca, Sr, and Mg in the structure are eluted. Along with this, there has been a problem that the interface between the resin and the inorganic filler peels off, or the insulation deteriorates 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 in order to improve the dispersibility in a resin.

Patent Documents

5 and 6 describe that a metal oxide such as barium titanate is surface-treated with a silane coupling agent in order to improve the mixing property with a resin.

International Publication No. 2005/093763 Japanese Patent Laid-Open No. 2003-49092 JP 2005-15652 A Unexamined-Japanese-Patent No. 7-240117 JP 2007-308345 A JP, 2017-199938, A

However, as examined by the present inventors, even if the surface of the perovskite-type composite oxide particle is simply treated with a coupling agent, the change in specific surface area with time or the elution of A site metal such as Ba is sufficiently reduced. It was found that there is still room for improvement in mixing with the resin. The homogeneous filling property to the resin and the affinity to the resin require good dispersibility in the organic solvent, and even if the perovskite type complex oxide is untreated or surface treated with a conventional coupling agent, It was difficult to obtain sufficient dispersion in an organic solvent.

Therefore, an object of the present invention is to provide a perovskite-type composite oxide excellent in packing property and dispersibility in a resin and a method for producing the same in order to solve the above-mentioned problems.

As a result of extensive research in view of the above situation, the present inventors have found that the perovskite type complex oxide coated with a specific silane coupling agent is excellent in dispersibility in an organic solvent, and is thus incorporated into a resin. It has been found that the packing property and the dispersibility are excellent, and the present invention has been completed.
That is, the present invention is a modified perovskite-type composite oxide in which the surface of a perovskite-type composite oxide particle is coated with a silane coupling agent represented by the following general formula (1).
(XY) _a Si (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, and 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, according to the present invention, after mixing the perovskite type complex oxide and the silane coupling agent represented by the above general formula (1), the mixture is supplied to an air flow crusher to obtain the perovskite type complex oxide. It is a method for producing a modified perovskite-type composite oxide, characterized in that the surface of the perovskite-type composite oxide particles is coated with the above-mentioned silane coupling agent while being pulverized.

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

It is a particle size distribution measurement result in the organic solvent of the modification | reformation barium titanate particle | grains obtained in Example 1. FIG. It is a particle size distribution measurement result in the organic solvent of the barium titanate particle | grains obtained by the comparative example 1. FIG. It is a particle size distribution measurement result in the water of the barium titanate particle obtained by the comparative example 1. FIG.

<Modified perovskite-type composite oxide>
The modified perovskite-type composite oxide of the present invention is obtained by coating the surface of a perovskite-type composite oxide particle with a silane coupling agent represented by the following general formula (1).
(XY) _a Si (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, and 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, potassium sodium niobate are not particularly limited. And bismuth potassium titanate, bismuth sodium titanate, bismuth ferrate, potassium tantalate, and as these composite solid solutions, potassium tantalate niobate, potassium sodium lithium tantalate niobate and the like can be mentioned. These perovskite complex oxides may be used alone or in combination of two or more.

The production history of such perovskite type complex oxide is not particularly limited, and, for example, coprecipitation method, hydrolysis method, wet method such as hydrothermal synthesis method, sol-gel method, solid phase method, etc. Those obtained by known methods are used. The physical properties of these perovskite type 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 It is preferable from the viewpoint of handling in the pulverizing step of 1 / g. The perovskite type composite oxide preferably has an average particle diameter of 0.1 μm to 10 μm, more preferably 0.15 μm to 5 μm from the viewpoint of handling in the pulverizing step. The average particle diameter is a median diameter (D50) measured using water as a dispersion medium by a laser diffraction scattering method.

The particle shape of the perovskite-type composite oxide to be modified is not particularly limited, and may be any of spherical, granular, plate-like, scaly, whisker-like, rod-like, filamentous, etc. .

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 to a common organic solvent, a hydrogen atom is preferable.

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 , 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. From the viewpoint of availability, the number of carbon atoms in the linear alkylene group is preferably 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. Further, 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.

Specific examples of the silane coupling agent represented by the general formula (1) include 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), nonyl trile Methoxysilane (X = hydrogen, Y = n-nonylene, Z = methyl, a = 1), decyltrimethoxysilane (X = hydrogen, Y = n-decylene, Z = methyl, a = 1) Decyltrimethoxysilane (X = hydrogen, Y = n-undecylene group, Z = methyl group, a = 1), dodecyltrimethoxysilane (X = hydrogen, Y = n-dodecylene group, Z = methyl group, a = 1 ), Tridecyl trimethoxy Orchid (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) and the like can be mentioned. Among these, hexyltrimethoxysilane, octyltriethoxysilane and decyltrimethoxysilane are preferable from the viewpoint of imparting dispersibility to a common organic solvent.

Average of the modified perovskite-type composite oxide (perovskite-type composite oxide coated with a silane coupling agent represented by the general formula (1)) of the present invention measured by using an organic solvent as a dispersion medium by a laser diffraction scattering method Average particle size (D50) of unmodified perovskite-type composite oxide (perovskite-type composite oxide before modification) measured using a particle size (D50) as Dos and using water as a dispersion medium by a laser diffraction scattering method When Dw is Dw, the degree of aggregation represented by Dos / Dw is preferably 1.4 or less, more preferably 1.2 or less. If the degree of aggregation is 1.4 or less, it means that it can be handled in the state of being dispersed in the organic solvent as well as the perovskite type complex oxide having relatively good wettability to water. The organic solvent to be used here is not particularly limited, and includes methyl ethyl ketone, acetone, n-hexane, methanol, ethanol, toluene, cyclopentanone and the like.

The moisture absorption of the modified perovskite-type composite oxide of the present invention is preferably 0.3% by mass or less, and more preferably 0.25% by mass or less. If the amount of moisture absorbed is 0.3% by mass or less, the degree to which the surface of the perovskite type complex oxide which is the base material is changed to hydroxide or carbonate compound by water is low, and the change of particle shape and deterioration of electric characteristics You can prevent. In the present specification, the moisture absorption amount of the modified perovskite-type composite oxide can be determined by the following method.
First, a sample of the modified perovskite complex oxide immediately after production is precisely weighed (A), and the dried product obtained by heating this sample in a tray drier at 105 ° C. for 2 hours is finely weighed (B ). Separately from this, a sample of the modified perovskite complex oxide immediately after production is precisely weighed (a), and this sample is allowed to absorb moisture by standing for 180 minutes in an environment of 40 ° C. and 90% humidity to obtain a hygroscopic sample obtained (C). The dried product obtained by heating this moisture-absorbing sample with a tray drier at 105 ° C. for 2 hours is precisely weighed (b). The amount of attached water is determined by the following equation to obtain the amount of moisture absorbed by the sample (% by mass).
Moisture content of moisture (mass%) = (((c-b) / a) x 100)-(((A-B) / A) x 100)

The modified perovskite complex oxide of the present invention is prepared by mixing the perovskite complex oxide to be modified and the silane coupling agent represented by the above general formula (1), and then subjecting the mixture to air flow grinding. It can be manufactured by coating the surface of the perovskite type complex oxide particles with a silane coupling agent while grinding the perovskite type complex oxide by supplying to a machine. A mixture of the perovskite complex oxide and the silane coupling agent represented by the above general formula (1) is supplied to an air flow crusher to newly form the perovskite complex oxide exposed in the process of being pulverized. Since the surface can be immediately coated with the silane coupling agent represented by the above general formula (1), the chance of exposure to the surrounding environment and contact with moisture can be reduced, and the elution and ratio of A-site metal can be reduced. The time-dependent change of the surface area can be suppressed.

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

As an air flow crusher, a jet mill, a stream mill, a fluidized bed crusher and the like can be mentioned. Among these, the jet mill is preferable from the viewpoint of less contamination due to the structure in which the blades and the media are not carried into the grinding chamber.

There are no particular limitations on the conditions for grinding using an air flow crusher, but the grinding pressure is preferably 0.03 MPa or more, and more preferably 0.05 MPa to 0.7 MPa. Further, the powder feeding speed is preferably 4 to 40 kg / hr, although it depends on the size of the air flow type crusher. By performing the pulverization conditions, the silane coupling agent represented by the above general formula (1) can be sufficiently and efficiently coated on the newly exposed surface of the perovskite-type composite oxide.

The modified perovskite-type composite oxide of the present invention thus obtained is excellent in the high dielectric characteristics, low loss characteristics, pyroelectric characteristics, piezoelectric characteristics, etc. It is possible to produce a composite dielectric material that The modified perovskite-type composite oxide of the present invention can be a ferroelectric, a pyroelectric and a piezoelectric, but in a broad sense it is generically called a dielectric including a paraelectric.

<Compound 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 contained in a polymer material described later preferably at least 60% by mass, more preferably at least 70% by mass to 90% by mass of the above modified perovskite-type composite oxide. More preferably, it is a material having a relative dielectric constant of 20 or more.

As a polymeric material which can be used in this invention, a thermosetting resin, a thermoplastic resin, or a photosensitive resin is mentioned.
As a thermosetting resin, for example, epoxy resin, phenol resin, polyimide resin, melamine resin, cyanate resins, bismaleimides, addition polymer of bismaleimides and diamine, polyfunctional cyanate ester resin, double resin Well-known things, such as bond addition polyphenylene oxide resin, unsaturated polyester resin, polyvinyl benzyl ether resin, a polybutadiene resin, fumarate resin, are mentioned. These thermosetting resins may be used alone or in combination of two or more. Among these thermosetting resins, epoxy resin and polyvinyl benzyl ether resin are preferable in terms of balance of heat resistance, processability, price and the like.

The epoxy resin used in the present invention is generally a monomer, an oligomer or a polymer having at least two epoxy groups in one molecule, for example, a phenol novolac epoxy resin, a phenol including an orthocresol novolac epoxy resin, Phenols such as cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde Epoxidized novolak resin obtained by condensation or cocondensation under an acidic catalyst, bisphenol A, bisphenol B, bisphenol F, bisphenol Diglycidyl ethers such as alkyl-substituted or unsubstituted biphenols, epoxidized adducts or polyadducts of phenols with dicyclopentadiene or terpenes, polybasic acids such as phthalic acid and dimer acids A glycidyl ester type epoxy resin obtained by the reaction of epichlorohydrin, a glycidyl amine type epoxy resin obtained by the reaction of epichlorohydrin with a polyamine such as diaminodiphenylmethane and isocyanuric acid, a linear form obtained by oxidizing an olefin bond with a peroxyacid such as peracetic acid Aliphatic epoxy resins, alicyclic epoxy resins and the like can be mentioned. These may be used singly or in combination of two or more.

As the epoxy resin curing agent, any of those known in the art can be used, and in particular, C ₂ to C ₂₀ linear aliphatic diamines such as ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc. Meta-phenylenediamine, para-phenylenediamine, para-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4 ' -Amines such as diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis (4-aminophenyl) cyclohexane and dicyanodiamide Species, pheno Novolak resin such as von novolak resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin, benzene ring such as polyoxystyrene such as resol type phenol resin, polyparaoxystyrene, phenol aralkyl resin, naphthol type aralkyl resin And a phenol resin obtained by co-condensing a carbonyl compound with a phenol compound in which a hydrogen atom bonded to a naphthalene ring or other aromatic ring is substituted with a hydroxyl group, an acid anhydride and the like. These may be used singly or in combination of two or more.
The compounding amount of the epoxy resin curing agent is preferably in the range of 0.1 to 10, more preferably 0.7 to 1.3 in equivalent ratio with respect to the epoxy resin.

In the present invention, a known curing accelerator may be used to accelerate the curing reaction of the epoxy resin. As a curing accelerator, for example, tertiary amine compounds such as 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, 2-methylimidazole, 2-ethyl-4- Examples thereof include imidazole compounds such as methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole, organic phosphine compounds such as triphenylphosphine and tributylphosphine, phosphonium salts, ammonium salts and the like. These may be used singly or in combination of two or more.

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 which may have a substituent, an aralkyl group, an aryl group or the like. 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. The hydrogen atom of R ₃ is derived from the starting compound in the synthesis of the compound of the general formula (2), and the curing reaction is carried out when the molar ratio of hydrogen atom to vinylbenzyl group is 60:40 to 0: 100. It can be sufficiently advanced, and is preferable in that sufficient dielectric characteristics can be obtained in the composite dielectric material of the present invention. n is an integer of 2 to 4;

The polyvinyl benzyl ether compound may be used by polymerizing it alone as a resin material, or may be used after being copolymerized with other monomers. Examples of copolymerizable monomers include styrene, vinyltoluene, divinylbenzene, divinylbenzyl ether, allylphenol, allyloxybenzene, diallyl phthalate, acrylic acid ester, methacrylic acid ester, vinyl pyrrolidone, modified products thereof, and the like. The blending ratio of these monomers is 2% by mass to 50% by mass with respect to the polyvinyl benzyl ether compound.

The polymerization and curing of the polyvinyl benzyl ether compound can be carried out by known methods. Curing may be either in the presence or absence of a curing agent. As a curing agent, for example, known radical polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl perbenzoate and the like can be used. The amount used is 0 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polyvinyl benzyl ether compound. The curing temperature varies depending on the use of the curing agent and the type of the curing agent, but is preferably 20 ° C. to 250 ° C., more preferably 50 ° C. to 250 ° C. for sufficient curing.
In addition, hydroquinone, benzoquinone, copper salts and the like may be blended for adjustment of curing.

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

As photosensitive resin, well-known thing, such as photopolymerizable resin and photocrosslinkable resin, is mentioned, for example.

As the photopolymerizable resin used in the present invention, for example, one containing an acrylic copolymer (photosensitive oligomer) having an ethylenically unsaturated group, a photopolymerizable compound (photosensitive monomer) and a photopolymerization initiator, epoxy The thing containing resin and a photocationic polymerization initiator etc. are mentioned. As a photosensitive oligomer, one obtained by adding acrylic acid to an epoxy resin, one obtained by reacting it with an acid anhydride, or (meth) acrylic acid is reacted with a copolymer containing a (meth) acrylic monomer having a glycidyl group. Further, those obtained by reacting an acid anhydride, those obtained by reacting a copolymer containing a (meth) acrylic monomer having a hydroxyl group with glycidyl (meth) acrylate, and those obtained by reacting an acid anhydride, A copolymer 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 may, for example, be mentioned. These may be used singly or in combination of two or more.

Examples of the photopolymerizable compound (photosensitive monomer) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, acryloyl morpholine, methoxypolyethylene glycol (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, N, N-dimethyl acrylamide, 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. These may be used singly or in combination of two or more.

Examples of the photopolymerization initiator include benzoin and its alkyl ethers, benzophenones, acetophenones, anthraquinones, xanthones, thioxanthones and the like. These may be used singly or in combination of two or more. These photopolymerization initiators can be used in combination with known and commonly used photopolymerization accelerators such as benzoic acid type and tertiary amine type. As a photocationic polymerization initiator, for example, triphenylsulfonium hexafluoroantimonate, diphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, benzyl 4-hydroxyphenylmethylsulfonium hexafluorophosphate, iron aroma of Bronsted acid Group compound salts (Ciba-Geigy, CG 24-061) and the like. These may be used singly or in combination of two or more.

Although an epoxy resin is ring-opening-polymerized by a photocationic polymerization initiator, the photopolymerization property is more preferable because an alicyclic epoxy resin has a faster reaction rate than a normal glycidyl ester epoxy resin. An alicyclic epoxy resin and a glycidyl ester epoxy resin can be used in combination. Examples of the alicyclic epoxy resin include vinylcyclohexene diepoxide, aryl cyclic diepoxy acetal, aryl cyclic diepoxy adipate, aryl cyclic diepoxy carboxylate, manufactured by Daicel Chemical Industries, Ltd., EHPE-3150, etc. Be These may be used singly or in combination of two or more.

Examples of the photocrosslinkable resin include water-soluble polymer dichromate-based, polyvinyl cinnamate (Kodak KPR), and cyclized rubber azide (Kodak KTFR). These may be used singly or in combination of two or more.

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 a higher dielectricity (eg, SDP-E (ε: 15 <) of Sumitomo Chemical, cyanoresin (Shin-Etsu Chemical It is also possible to add ε: 18 <)) or a high dielectric liquid (eg, SDP-S (ε: 40 <) from Sumitomo Chemical).

In the present invention, the above-described polymer materials may be used singly or in combination of two or more.
In the composite dielectric material of the present invention, the compounding amount of the modified perovskite-type composite oxide is preferably 60% by mass or more, more preferably 70% by mass to 90% by mass, as a ratio occupied at the time of complexing with the resin. The reason is that if the amount is less than 60% by mass, a sufficient relative dielectric constant tends not to be obtained, while if it exceeds 90% by mass, the viscosity tends to increase and the dispersibility tends to be poor. This is because there is a concern that the strength can not be obtained. It is desirable that the material has a relative dielectric constant of preferably 15 or more, more preferably 20 or more according to the above composition.

In addition, the composite dielectric material of the present invention can contain other fillers in an amount 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, silicon carbide and the like.

In addition, the composite dielectric material of the present invention, as long as the effects of the present invention are not impaired, curing agents, glass powders, polymer additives, reactive diluents, polymerization inhibitors, leveling agents, wettability improvers, Even if surfactant, plasticizer, UV absorber, antioxidant, antistatic agent, inorganic filler, antifungal agent, humidity control agent, dye solubilizer, buffer agent, chelating agent, flame retardant, etc. are added Good. These additives may be used alone or in combination of two or more.

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

The composite dielectric paste contains a resin component, a modified perovskite-type composite oxide, an additive which is optionally added, 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 combining 2 or more types.

Here, the polymerizable compound means a compound having a polymerizable group, and includes, for example, a precursor polymer before complete curing, a polymerizable oligomer and a monomer. Moreover, a polymer shows the compound in which the polymerization reaction was substantially completed.

The organic solvent to be added if necessary varies depending on the resin component to be used, and is not particularly limited as long as it can dissolve the resin component, for example, N-methylpyrrolidone, dimethylformamide, ether, diethyl ether, tetrahydrofuran Dioxane, ethyl glycol ether of monoalcohol having linear or branched alkyl group having 1 to 6 carbon atoms, propylene glycol ether, butyl 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 carbonization Group and an aromatic hydrocarbon 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 used after being adjusted 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 preferably 10,000 mPa · s to 600 in consideration of the coatability of the composite dielectric paste. And 000 mPa · s (25 ° C.).

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

In order to produce a composite dielectric film using the composite dielectric material of the present invention, it may be produced, for example, according to the conventionally known method of using a composite dielectric paste, and an example thereof is shown below.
After the composite dielectric paste is applied on a substrate, it can be formed into a film by drying. As a base material, for example, a plastic film whose surface is subjected to a peeling treatment can be used. When it apply | coats on the plastic film in which the peeling process was performed, and it shape | molds in a film form, generally it is preferable to peel and use a base material from a film after shaping | molding. As a plastic film which can be used as a base material, films of polyethylene terephthalate (PET) film, polyethylene film, polypropylene film, polyester film, polyimide film, aramid, kapton, polymethylpentene and the like can be mentioned. 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. Moreover, as a mold release process given on the base-material surface, the mold release process which apply | coats silicone, a wax, a fluorine resin etc. on the surface is used preferably.

Alternatively, a metal foil may be used as a substrate, and a dielectric film may be formed on the metal foil. In such a case, the metal foil used as a base material can be used as an electrode of a capacitor.

It does not specifically limit as method to apply | coat the said composite dielectric paste on a base material, 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 heated and thermally cured after being incorporated into a substrate such as a printed circuit board. Moreover, when photosensitive resin is used, it can pattern by selectively exposing.

Also, for example, the composite dielectric material of the present invention may be extruded and formed into a film by a calender method or the like.
The extruded dielectric film may be shaped to be extruded onto the above-described substrate. Moreover, when using metal foil as a base material, in addition to the foil made from copper, aluminum, brass, nickel, iron etc. as a metal foil, foil of these alloys, composite foil etc. can be used. The metal foil may be subjected to a surface roughening treatment, an application of an adhesive, or the like as required.

Also, a dielectric film may be formed between the metal foils. In this case, after the composite dielectric paste is applied on the metal foil, the metal foil is placed on the metal foil and dried in a state where the composite dielectric paste is sandwiched between the metal foils, thereby being sandwiched between the metal foils. It is also possible to form a dielectric film in the negative state. Alternatively, the dielectric film provided between the metal foils may be formed by extrusion so as to be sandwiched between the metal foils.

In addition, the composite dielectric material of the present invention may be used as a prepreg by forming a varnish using the above-mentioned organic solvent, impregnating it with a cloth or a non-woven fabric, and drying it. The type of cloth or non-woven fabric that can be used is not particularly limited, and known ones can be used. Examples of the cloth include glass cloth, aramid cloth, carbon cloth, stretched porous polytetrafluoroethylene and the like. Moreover, as a nonwoven fabric, an aramid nonwoven fabric, glass paper, etc. are mentioned. The prepreg can be introduced into the electronic component by laminating it on an electronic component such as a circuit board and then curing it.

Since the composite dielectric material of the present invention has a high relative dielectric constant, it can be suitably used as a dielectric layer of an electronic component, particularly a printed circuit board, a semiconductor package, a capacitor, an antenna for high frequency, an inorganic EL etc. it can.

In order to produce a multilayer printed wiring board using the composite dielectric material of the present invention, it can be produced using a method known in the relevant technical field (for example, JP-A 2003-192768, JP-A 2005- 29700, JP-A 2002-226816, JP-A 2003-327827, etc.). In addition, an example shown below is an illustration at the time of using a thermosetting resin as a polymeric material of composite dielectric material.

The composite dielectric material of the present invention is used as the above-mentioned dielectric film, and the circuit board of the dielectric film is pressed, heated or laminated using a vacuum laminator. After lamination, a metal foil is further laminated on the resin layer exposed by peeling off the substrate from the film, and the resin is heat-cured.

Moreover, although the composite dielectric material of this invention is made into a prepreg, lamination to the circuit board can be performed by a vacuum press. Specifically, it is desirable that one side of the prepreg be in contact with the circuit board, and metal foil be placed on the other side for pressing.

In addition, the composite dielectric material of the present invention is used as a varnish, and the circuit board is coated and dried using screen printing, curtain coating, roll coating, spray coating or the like to form an intermediate insulating layer of a multilayer printed wiring board be able to.

In the present invention, in the case of a printed wiring board having an insulating layer as the outermost layer, through holes and via holes are drilled or drilled by a laser, and the surface of the insulating layer is roughened to form fine irregularities. The method of roughening the insulating layer may be carried out according to the specification 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 it can. Specific examples of the roughening agent include dichromates, permanganates, ozone, oxidizing agents such as hydrogen peroxide / sulfuric acid and nitric acid, N-methyl-2-pyrrolidone, N, N-dimethylformamide, methoxy Organic solvents such as propanol, alkaline aqueous solutions such as caustic soda and potassium hydroxide, acidic aqueous solutions such as sulfuric acid and hydrochloric acid, or various plasma treatments can be used. Also, these processes may be used in combination. As described above, on the printed wiring board on which the insulating layer is roughened, 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 pattern reverse to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. By annealing after the conductor layer is formed as described above, curing of the thermosetting resin proceeds and the peel strength of the conductor layer can be further improved. Thus, the conductor layer can be formed on the outermost layer.

Moreover, the metal foil in which the intermediate | middle insulating layer was formed can be multilayered by laminating | stacking by a vacuum press. The metal foil in which the intermediate insulating layer is formed can be made into a printed wiring board in which the outermost layer is a conductor layer by laminating on the printed wiring board on which the inner layer circuit is formed by a vacuum press. Moreover, the prepreg using the composite dielectric material of the present invention is a printed wiring board in which the outermost layer is a conductor layer by laminating with a metal foil by a vacuum press on a printed wiring board on which an inner layer circuit is formed. Can be Predetermined through holes and via holes are drilled or lasered by a conformal method or the like, and the insides of the through holes and via holes are desmeared to form fine irregularities. Next, the layers are electrically connected by wet plating such as electroless and electrolytic plating.

Furthermore, if necessary, these steps are repeated several times, and after the circuit formation of the outermost layer is completed, the solder resist is subjected to screen printing, pattern printing, heat curing, or curtain coating, roll coating, or spray coating. A desired multilayer printed wiring board is obtained by forming a pattern with a laser after printing on the entire surface and heat curing.

Hereinafter, the present invention will be described in more detail by way of 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 resulting suspension was stirred at a temperature of 55 ° C. for 0.5 hours to give a solution A. A solution B was prepared by adding 5600 g of pure water to 2560 g of a 15.3% by mass aqueous solution of titanium tetrachloride in terms of TiO ₂ and diluting it.
Then, while stirring, Solution B was added to Solution A over 30 minutes at a reaction temperature of 55 ° C., and after addition, aging was performed for 0.5 hours while stirring was continued. After the completion of aging, it was filtered to recover barium titanyl oxalate.
Then, the collected barium titanyl oxalate was repulped with pure water and allowed to stand and dried at 80 ° C. for 24 hours to obtain barium titanyl oxalate powder.
500 g of the obtained barium titanyl oxalate powder is charged in an alumina crucible, calcined at 900 ° C. for 10 hours, pulverized by a jet mill, and further calcined at 900 ° C. for 9 hours to obtain barium titanate (BET specific surface area : 9 m ² / g, average particle size: 0.5 μm).

[Examples 1 to 3]
A silane coupling agent of the type and amount shown in Table 1 is sprayed onto 200 g of the barium titanate obtained above to obtain a mixture of barium titanate and a silane coupling agent, and this mixture is jet mill (( 2.) A modified barium titanate was produced by supplying to SEISIN STJ 200) and processing under the condition of grinding pressure 0.060.06 MPa.

Comparative Example 1
The barium titanate obtained above was supplied to a jet mill without spraying a silane coupling agent, and was processed under the conditions of grinding pressure 0.060.06 MPa to produce crushed 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 surface treatment agent was changed to the type and amount shown in Table 1.

<Evaluation>
(Cohesion degree)
The average particle diameter (D50) of the barium titanate not subjected to the surface treatment with the silane coupling agent of Comparative Example 1 was determined by a laser diffraction scattering method using water as a dispersion medium. The average particle size at this time was taken as Dw. Next, with respect to the modified barium titanates of Examples 1 to 3 and Comparative Examples 2 to 4 and the barium titanate of Comparative Example 1, using methyl ethyl ketone as a dispersion medium, the average particle diameter (D50) is determined by the laser diffraction scattering method The The average particle size at this time was taken as Dos.
Dos / Dw was calculated from the obtained measured value, and it was considered as the degree of aggregation of particles in the organic solvent. The results are shown in Table 2. The particle size distribution measurement in an organic solvent of the modified barium titanate particles obtained in Example 1 is shown in FIG. 1, and the particle size distribution measurement in an organic solvent of the barium titanate particles obtained in Comparative Example 1 is shown. The result is shown in FIG. 2, and the particle size distribution measurement result in water of the barium titanate particles obtained in Comparative Example 1 is shown in FIG. For measurement of the average particle size, a laser diffraction type particle size distribution measuring apparatus (manufactured by Microtrac Bell, MT3300EX) was used.

(Dissolution test)
2 g of the sample obtained in each of Examples 1 to 3 and Comparative Examples 1 to 4 and 50 g of ion exchanged water were precisely weighed and stirred for 1 hour, and the supernatant was filtered with a 0.2 μm pore diameter syringe filter to make 20 g of filtrate Then, 1 mL of concentrated hydrochloric acid was added, and the volume of the sample solution adjusted to 50 mL was quantified with ICP-AES (Agilent 5100, Agilent) to evaluate the elution of Ba into water. The results are shown in Table 2.

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

From the results in Table 2, in the barium titanate of Comparative Example 1 and the modified barium titanate with the titanium coupling agent of Comparative Example 2, the degree of aggregation in the organic solvent was high. Further, in the modified barium titanate of Comparative Example 3 and Comparative Example 4, the elution amount of Ba and the moisture absorption amount were large. On the other hand, in the modified barium titanate obtained in Examples 1 to 3, the degree of aggregation is low, the elution of Ba is suppressed, and the amount of hygroscopic water is small, resulting in stabilized particles. It can be understood that

<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 the suspension obtained by stirring at a temperature of 55 ° C. for 0.5 hours was designated as solution A. A solution B was prepared by adding 5600 g of pure water to 2560 g of a 15.3% by mass aqueous solution of titanium tetrachloride in terms of TiO ₂ and diluting it.
Then, while stirring, Solution B was added to Solution A over 30 minutes at a reaction temperature of 55 ° C., and after addition, aging was performed for 0.5 hours while stirring was continued. After the completion of aging, it was filtered to recover strontium titanyl oxalate.
Then, the recovered strontium titanyl oxalate was repulped with pure water and allowed to stand and dried at 80 ° C. for 24 hours to obtain a powder of strontium titanyl oxalate.
500 g of the obtained powder of strontium titanyl oxalate is put in an alumina crucible, calcined at 900 ° C. for 10 hours, pulverized by a jet mill, and further calcined at 900 ° C. for 9 hours to obtain strontium titanate (BET specific surface area 11 m ² / g, average particle size: 0.4 μm).

[Examples 4 to 6]
A silane coupling agent of the type and amount shown in Table 3 is sprayed onto 200 g of the strontium titanate obtained above to obtain a mixture of strontium titanate and a silane coupling agent, and this mixture is jet mill (( 2.) The solution was supplied to Seishin Enterprise Co., Ltd., STJ 200, and treated under the conditions of grinding pressure 0.06 0.06 MPa to produce modified strontium titanate.

Comparative Example 5
The strontium titanate obtained above was supplied to a jet mill without spraying a silane coupling agent, and was processed under the conditions of grinding pressure 0.060.06 MPa to produce crushed 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 surface treatment agent was changed to the type and amount shown in Table 3.

<Evaluation>
(Cohesion degree)
The degree of aggregation 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.

(Dissolution test)
In the same manner as in Examples 1 to 3 and Comparative Examples 1 to 4, the evaluation of Sr elution in water of the samples obtained in Examples 4 to 6 and Comparative Examples 5 to 8 was performed. The results are shown in Table 4.

(Moisture absorption test)
The moisture absorption amount of each 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.

From the results in 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 the organic solvent was high, and the elution amount of Sr and the moisture absorption amount were large. On the other hand, in the modified strontium titanate obtained in Examples 4 to 6, the degree of aggregation is low, the elution of Sr is suppressed, and the amount of hygroscopic water is small, resulting in stabilized particles. It can be understood that

Preparation of potassium sodium niobate
A raw material mixture was obtained by dry mixing 4688 g of niobium pentoxide, 958 g of sodium carbonate and 1183 g of potassium carbonate using a Henschel mixer.
The raw material mixture is calcined at 650 ° C. for 7 hours, pulverized by a jet mill, and further calcined at 900 ° C. for 10 hours to obtain potassium sodium niobate (BET specific surface area: 3 m ² / g, average particle size: 0.9 μm) was obtained.

[Example 7]
A silane coupling agent of the type and amount shown in Table 5 is sprayed onto 200 g of potassium sodium niobate obtained above to obtain a mixture of potassium sodium niobate and a silane coupling agent, and this mixture is jet milled ( It supplied to Seishin Enterprise Co., Ltd. (STJ200), processed on the conditions of grinding pressure> = 0.06MPa, and modified potassium sodium niobate was manufactured.

Comparative Example 9
The potassium sodium niobate obtained above was supplied to a jet mill without spraying a silane coupling agent, and was processed under the conditions of grinding pressure 0.060.06 MPa to produce ground potassium sodium niobate.

<Evaluation>
(Cohesion degree)
The degree of aggregation of the samples obtained in Example 7 and Comparative Example 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.

(Dissolution test)
The evaluation of Sr elution in water of the samples obtained in Example 7 and Comparative Example 9 was performed 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 absorption amount of each of the samples obtained in Example 7 and Comparative Example 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.

From the results in Table 6, in the potassium sodium niobate of Comparative Example 9, the degree of aggregation in the organic solvent was high, and the elution amounts of Na and K and the moisture absorption amount were large. On the other hand, in the modified potassium sodium niobate obtained in Example 7, the degree of aggregation is low, the elution of Na and K is suppressed, and the amount of hygroscopic water is small, resulting in stabilized particles. It is understood that

This international application claims priority based on Japanese Patent Application No. 2017-243790 filed on Dec. 20, 2017, and the entire content of this Japanese patent application is incorporated into this international application. Do.

Claims

A modified perovskite-type composite oxide, wherein the surface of a perovskite-type composite oxide particle is coated with a silane coupling agent represented by the following general formula (1).
(XY) a Si (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, and 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 average particle diameter (D50) of the modified perovskite complex oxide measured by using an organic solvent as a dispersion medium by a laser diffraction scattering method as Dos, and not measured by using water as a dispersion medium by a laser diffraction scattering method The modified perovskite according to claim 1, characterized in that the degree of aggregation represented by Dos / Dw is 1.4 or less, where Dw is an average particle diameter (D50) of the porous perovskite type composite oxide. Type complex oxide.
The modified perovskite-type composite oxide according to claim 1 or 2, wherein the moisture absorption amount is 0.3 mass% or less.
The perovskite type complex oxide is barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, sodium potassium niobate, lithium potassium sodium niobate, bismuth potassium titanate, bismuth sodium titanate, iron The modified perovskite-type composite oxide according to any one of claims 1 to 3, which is bismuth acid, potassium tantalate or a composite solid solution thereof.
A perovskite type composite oxide and a silane coupling agent represented by the following general formula (1) are mixed, and then the mixture is supplied to an air flow crusher to crush the perovskite type composite oxide while being crushed. A method for producing a modified perovskite-type composite oxide, comprising coating the surface of the composite oxide particle with the silane coupling agent.
(XY) a Si (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, and 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.)
6. The modified perovskite type according to claim 5, wherein the mass ratio of the perovskite type complex oxide to the silane coupling agent during the mixing is 99.5: 0.5 to 95: 5. Method of producing complex oxide.
The method for producing a modified perovskite-type composite oxide according to claim 5 or 6, wherein the air flow crusher 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 the surface treatment by the air flow type pulverizer are performed at a grinding pressure of 0.03 MPa or more.
The perovskite type complex oxide is barium titanate, strontium titanate, calcium titanate, potassium niobate, sodium niobate, sodium potassium niobate, lithium potassium sodium niobate, bismuth potassium titanate, bismuth sodium titanate, iron The method for producing a modified perovskite-type composite oxide according to any one of claims 5 to 8, which is bismuth acid, potassium tantalate or a composite solid solution thereof.
A composite dielectric material comprising the modified perovskite-type composite oxide according to any one of claims 1 to 4 and a polymer material.