JP2002231052A - Complex particles for dielectric substance, dielectric substance forming composition, and electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable to form a dielectric layer with low dielectric loss tangent of 0.1 or less, and high dielectric constant of 30 or more, at low heating temperature of 500 deg.C or less. SOLUTION: The dielectric substance forming composition is able to form a dielectric substance with low dielectric loss tangent of 0.1 or less and high dielectric constant of 30 or more, at low heating temperature of 500 deg.C or less, which is composed of at least one resin component of either the complex particles for dielectric substance covered by conductive metal or its compound, or conductive organic compound or conductive inorganic material; or a polymerized compound and a polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite particle for a dielectric, a composition for forming a dielectric containing the composite particle for a dielectric, an aqueous dispersion or a dielectric paste for electrodeposition containing the composition, the composition, The present invention relates to a high dielectric constant film formed from an aqueous electrodeposition liquid dispersion or a dielectric paste, and an electronic component including the high dielectric constant film.

[0002]

2. Description of the Related Art In recent years, a technique has been known in which a layer having a high dielectric constant is provided on a multilayer printed wiring board or the like, and this layer is used for a capacitor or the like. This high dielectric constant layer can be, for example,
An organic solvent solution containing a thermosetting resin and an inorganic powder with a high dielectric constant added is impregnated into a fiber reinforcing material such as glass fiber to compensate for the brittleness of the thermosetting resin, and the solvent is scattered by firing or the like. It is prepared by a method such as curing after curing. However, it is usually difficult to obtain a layer having a high dielectric constant of, for example, 30 or more or 50 or more by the conventional method.

Attempts have also been made to obtain a dielectric layer having a high dielectric constant by using various inorganic powders. For example, when Fe ₃ O ₄ or ZnO + carbon is added as an inorganic powder to polystyrene, a dielectric layer having a high dielectric constant is obtained. It is known that a body layer can be obtained. But in such a system,
Even if the dielectric constant can be increased, the dielectric loss tangent of the obtained dielectric layer is increased, so that the heat generated in the dielectric layer in an AC electric field is increased, such as in a multilayer printed wiring board provided with a dielectric film. There is a problem that deterioration and thermal stress may cause a failure such as breakage of a joint portion, and the reliability and durability of the semiconductor substrate are easily reduced.

On the other hand, to obtain a high dielectric constant, usually,
A method of forming a dielectric layer by heating and baking an inorganic powder having a high dielectric constant at a high temperature is known. However, this method
For example, since it is necessary to bake at a high temperature of about 1000 ° C., it cannot be applied to a case where a dielectric layer is provided in a state where an electronic component is mounted on a wiring board, and is generally used for various semiconductor substrate manufacturing processes. There was a problem that it could not be applied.

[0005] For this reason, it has been desired to provide a dielectric layer having a high dielectric constant and a small heat loss by firing at a low temperature, and the appearance of inorganic particles and compositions capable of providing such a dielectric layer. Therefore, the present inventors have intensively studied to solve the above-mentioned problem, and a part or the entire surface of a specific inorganic particle, a particle containing a particle coated with a conductive metal or an organic compound, and a resin component It has been found that by using a composition consisting of the following, calcination can be performed at a low temperature of 500 ° C. or less, and a dielectric having a high dielectric constant and a low dielectric loss tangent can be formed, and the present invention has been completed.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art described above, and it is an object of the present invention to provide an inorganic material capable of forming a dielectric layer having a small heat loss and a high dielectric constant which can be fired at a low temperature. It is an object of the present invention to provide particles, a composition for forming a dielectric, a high dielectric constant film formed from the composition, and an electronic component provided with the high dielectric constant film.

[0007]

SUMMARY OF THE INVENTION A composite particle for a dielectric according to the present invention comprises a conductive metal or a compound thereof, a conductive organic compound or a conductive organic compound on a part or the whole of the surface of an inorganic particle having a dielectric constant of 30 or more. Characterized by being coated with an inorganic substance. The inorganic particles are preferably made of a titanium-based metal oxide. Further, the titanium-based metal oxide is preferably a double oxide.

[0008] The average particle diameter of the composite particles for a dielectric is 1
It is preferably 0 μm or less. The dielectric-forming composition according to the present invention has a dielectric constant of 30 when heated to 500 ° C. or lower.
As described above, it is possible to form a dielectric material having a dielectric loss tangent of 0.1 or less, and a conductive metal or a compound thereof or a conductive metal on a part or the entire surface of the inorganic particles having a dielectric constant of 30 or more. It is characterized by comprising dielectric composite particles coated with an organic compound or a conductive inorganic substance, and a resin component comprising at least one of a polymerizable compound and a polymer.

The dielectric obtained by heating the composition for forming a dielectric at 500 ° C. or lower preferably has a dielectric constant of 50 or more and a dielectric loss tangent of 0.1 or less. The inorganic particles are preferably made of a titanium-based metal oxide. Further, it is preferable that the titanium-based metal oxide is a titanium-based double oxide. The average particle size of the composite particles for a dielectric is preferably 10 μm or less.

The volume ratio of the composite particles for dielectric material to the resin component comprising at least one of the polymerizable compound and the polymer (volume of composite particles for dielectric material / the resin comprising at least one of the polymerizable compound and the polymer) Component volume)
It is preferably 5/95 to 80/20. The dielectric forming composition may further contain a filler.

The dielectric paste according to the present invention is a paste containing the composition for forming a dielectric. in this case,
Preferably, the resin component is a thermosetting resin that is a polymerizable compound, and the polymer is a thermoplastic resin.
The aqueous dispersion for electrodeposition according to the present invention is an aqueous dispersion containing the composition for forming a dielectric. In this case, the resin component composed of at least one of the polymerizable compound and the polymer is preferably an electrodepositable organic particle. Further, it is preferable that the organic particles are made of a polyimide resin and have a charge on the surface of the organic particles.

[0012] The high dielectric constant film according to the present invention is characterized in that it is formed using the composition for forming a dielectric. The high dielectric constant film of the present invention is characterized by being formed using the dielectric paste or the aqueous dispersion for electrodeposition. In the method for producing a dielectric according to the present invention, a part or all of the surface of the inorganic particles having a dielectric constant of 30 or more is coated with a conductive metal or a compound thereof or a conductive organic compound or a conductive inorganic substance. Dielectric composite particles that are, a composition containing a resin component consisting of at least one of a polymerizable compound and a polymer,
It is characterized in that a dielectric having a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less is obtained by heating at 500 ° C. or less.

An electronic component according to the present invention is characterized by including the high dielectric constant film.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. [Composite Particles for Dielectric] Inorganic Particles The inorganic particles used in the present invention have a dielectric constant of 30 or more, preferably 50 or more, more preferably 70 or more. Although the dielectric constant is high, there is no problem, and the upper limit is not limited. For example, it may be about 30,000.

As such inorganic particles, those composed of metal oxides are preferably used, and titanium-based metal oxides are particularly preferred. Here, “titanium-based metal oxide” refers to a compound containing a titanium element and an oxygen element as essential elements. As such a titanium-based metal oxide, a titanium-based single metal oxide containing titanium as a single metal element constituting a crystal structure, and a titanium-based double oxide containing titanium and other metal elements as a metal element Are preferably used.

The titanium-based single metal oxide includes, for example, a titanium dioxide-based metal oxide. Examples of such a titanium dioxide-based metal oxide include titanium dioxide-based metal oxides having an anatase structure or a rutile structure. Examples of the titanium-based double oxide include:
Metal oxides such as barium titanate, lead titanate, strontium titanate, bismuth titanate, magnesium titanate, neodymium titanate, and calcium titanate can be used.

The above-mentioned "titanium dioxide-based metal oxide"
The term refers to a system containing only titanium dioxide or a system containing a small amount of other additives to titanium dioxide, which retains the crystal structure of the main component, titanium dioxide, and a metal of another system. The same applies to oxides. In addition, the “titanium-based composite oxide” is an oxide formed by combining a titanium-based single metal oxide and a metal oxide composed of at least one other metal element. Oxic acid ion does not exist.

In the present invention, as the titanium-based metal oxide constituting such inorganic particles, among the titanium-based single metal oxides, a titanium dioxide-based metal oxide having a rutile structure is preferable. Among the oxides, barium titanate-based metal oxides can be preferably used. Among these, a barium titanate-based metal oxide can be particularly preferably used.

In order to improve the dispersibility in an aqueous medium, particles obtained by modifying the surface of the inorganic particles with silica, alumina or the like can also be used preferably. The average particle diameter of such inorganic particles is preferably 10 μm or less, more preferably 5 μm or less, more preferably 1 μm or less, and particularly preferably 0.7 μm or less. If the average particle diameter exceeds 10 μm, the composition of the dielectric layer may be likely to be non-uniform when the film thickness is reduced. Although the lower limit of the average particle size is not particularly limited, it is usually 0.02.
μm or more. The shape of the inorganic particles of the present invention is not particularly limited, but examples include spherical, granular, plate-like, scale-like, whisker-like, rod-like, and filament-like shapes. Among these shapes, it is preferable that the shape is spherical, granular, flaky, or scaly. These inorganic particles can be used alone or in combination of two or more. The composite particles for a dielectric used in the present invention are partially or entirely the surface of the inorganic particles, a conductive metal or a compound thereof, or a conductive organic compound or a conductive inorganic material. Coated.

As the conductive metal, for example,
Gold, silver, copper, tin, platinum, palladium, ruthenium, Fe,
At least one metal selected from Ni, Co, Ge, Si, Zn, Ti, Mg, Al and the like can be used. These alloys can also be used as the metal. As the conductive metal compound, a nitride of the conductive metal can be used.

As the conductive organic compound, TCN is used.
At least one compound selected from Q (7,7,8,8-tetracyanoquinodimethane), polypyrrole, polyaniline, polythiophene and the like can be used. As the conductive inorganic substance, at least one selected from carbon, graphite, and the like can be used.

The ratio of the inorganic particles contained in the composite particles for dielectric used in the present invention is preferably 70 to 99% by weight, more preferably 85 to 95% by weight, based on the total weight of the composite particles for dielectric. %, Particularly preferably 80 to 90% by weight. The ratio of the conductive metal or conductive organic compound is preferably 1
It is desirable that it is contained in an amount of from 30 to 30% by weight, more preferably from 5 to 15% by weight, particularly preferably from 10 to 20% by weight.

If the proportion of the inorganic particle component exceeds 99% by weight, a high dielectric constant may not be obtained when the dielectric material is used. When the proportion of the inorganic particle component is less than 70% by weight, the insulating properties of the dielectric may be deteriorated. The average particle diameter of the composite particles for a dielectric used in the present invention is preferably 10 μm or less, more preferably 5 μm or less, more preferably 1 μm or less, and particularly preferably 0.7 μm or less. If the average particle diameter exceeds 10 μm, the composition of the dielectric layer may be likely to be non-uniform when the film thickness is reduced. The average particle size of the composite particles for a dielectric is preferably 1 μm or less in order to make the composition of the dielectric layer uniform even when the film thickness is reduced. The lower limit of the average particle diameter is not particularly limited, but is usually 0.02 μm or more.

The composite particles for a dielectric used in the present invention can be prepared by a known method and are not limited. For example, when a conductive metal is coated on the surface of the inorganic particles by plating or the like, it can be performed by electroless plating such as chemical plating. Also, for example,
By a known method such as a gas atomizing method, the surface of the inorganic particles can be coated with a conductive metal or an organic compound in an alloy state or in a composite state. Furthermore, in the composite particles for a dielectric prepared by the gas atomization method, the oxidation of the particle surface can be suppressed by increasing the concentration of the conductive component near the particle surface using, for example, a known alloy manufacturing method.

More specifically, composite particles for dielectrics consisting of inorganic particles coated with a metal component of 1 to 40% by weight are collected by a classifier to obtain a powder having an average particle size of 1 to 10 μm. After ultrasonically dispersing in water and sufficiently immersing the surface, only the Cu content on the surface is eluted in a 1 to 10% by volume sulfuric acid bath to obtain composite particles for a dielectric.

Also, for example, even if the particles are fine or flaky, composite particles containing a large amount of conductive components near the surface of the dielectric composite particles can be produced.
In such composite particles for dielectrics, 3 to inorganic particles are used.
５０50% by weight of carbon can be added and carbon can be mechanically attached to the magnetic powder while being pulverized (mechanochemical method).

Further, the concentration of the conductive component in the vicinity of the surface of the composite particles for a dielectric material can be made higher than the average concentration by melting the conductive metal and the inorganic particles in a high-temperature plasma gas and then rapidly solidifying them. be able to. When obtaining fine powder of composite particles for a dielectric material having an average particle diameter of about 0.1 to 10 μm, the inorganic particles in a fine powder form are dispersed into primary particles by fluid jet milling in an inert atmosphere, The inorganic particles obtained by the dispersion treatment are heat-treated under reduced pressure in an inert atmosphere, and the heat-treated inorganic particles are charged into a rotating container containing a conductive component as a sputtering source, and the container is rotated in a certain direction. Then, a fluidized bed of inorganic particles is formed, and a coating (coating) material is coated on the fluidized inorganic particles by sputtering a conductive component while rotating the container, and the coated fine powder is introduced with an inert gas and vacuum. By taking out from the rotating container on the principle of a vacuum cleaner by combining exhaust, within the range of the average particle diameter, the surface of the inorganic particles is coated with a conductive component firmly and uniformly for a dielectric material. It can also be obtained if particles.

[Dielectric Forming Composition] The dielectric forming composition according to the present invention comprises the dielectric composite particles and a resin component comprising at least one of a polymerizable compound and a polymer. Such a composition for forming a dielectric can be formed by heating the composition at 500 ° C. or lower to form a dielectric or a dielectric having a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less. Things.

In this specification, the dielectric constant and the dielectric loss tangent are values measured by the method described in JIS K6481 (frequency 1 MHz). Further, the composition for forming a dielectric may further contain other fillers as necessary. In the present invention, the volume ratio of the composite particles for a dielectric to the resin component comprising at least one of the polymerizable compound and the polymer (volume of the composite particles for a dielectric / consisting of at least one of the polymerizable compound and the polymer) The volume of the resin component) is preferably 5/95 to 80/20, and more preferably 10/90 to 60/40.
If the ratio of the composite particles for a dielectric is less than 5% by volume, it may be difficult to obtain a dielectric having a high dielectric constant. When the ratio of the composite particles for a dielectric exceeds 80% by volume,
When the dielectric is in the form of a film, the film-forming property of the film may be deteriorated.

In the present invention, the weight ratio of the composite particles for dielectric material to the resin component comprising at least one of the polymerizable compound and the polymer (weight of the composite particles for dielectric material /
Weight of the resin component comprising at least one of a polymerizable compound and a polymer) is preferably 60/40 to 95/5,
More preferably, the ratio is 70/30 to 90/10. If the ratio of the composite particles for a dielectric is less than 60% by weight, it may be difficult to obtain a dielectric having a high dielectric constant. If the ratio of the composite particles for a dielectric exceeds 95% by weight, the film-forming property of the film may be deteriorated when the dielectric is in the form of a film.

Resin Component The resin component that can be used in the present invention comprises at least one of a polymerizable compound and a polymer. Here, the “polymerizable compound” refers to a compound having a polymerizable group, and means a compound including a precursor polymer, a polymerizable oligomer, a monomer, and the like before complete curing. The term “polymer” means a compound in which a polymerization reaction has been substantially completed. However, it is also possible to crosslink the polymer after the formation of the dielectric layer by heating, moisture and the like.

In the present invention, the preferred resin component differs depending on whether the dielectric composition is used as (1) a dielectric paste or (2) an aqueous dispersion for electrodeposition, which will be described later. Will be described. (1) Resin Component for Dielectric Paste (Resin Component (1)) The dielectric paste of the present invention contains a composition for forming a dielectric and can contain an organic solvent as required. That is,
When the dielectric forming composition is in the form of a paste, it can be used as it is as a dielectric paste, and the constituent resin component is dissolved in an organic solvent, and the dielectric composite particles are dispersed therein, and the paste is formed. Can also be used. When the composition for forming a dielectric material of the present invention is used as a dielectric paste, a resin component may be used under certain conditions.
The dielectric paste is not particularly limited as long as it does not impair the adhesion of the semiconductor to the printed wiring board or the like.

As such a resin component, it is possible to print a paste on a target substrate or the like and then heat the resin component by heating to cure the resin component, and to bake the resin by heating. Thermoplastic type (A2)
And the resin component (1) can be preferably used. These can be used alone or in combination. When both the polymerizable compound and the polymer are used as the resin component, the polymerizable compound is preferably a thermosetting resin, and the polymer is preferably a thermoplastic resin. When resins are used together in such a combination, slight shrinkage of the resin component due to heating can be reduced, and even when a dielectric layer is formed on a circuit board as a film, a film having excellent positional accuracy can be obtained. Obtainable. Hereinafter, these resin components will be described in more detail. (A1) Resin component (thermosetting type) As the thermosetting type resin component, (A1-a) a weight average molecular weight (referred to as a polystyrene equivalent weight average molecular weight by a gel permeation method; hereinafter the same) is 300 to 300.
Structural units derived from an epoxy resin within the range of 5,000 and / or a compound having an ethylenic double bond and an epoxy group in one molecule (hereinafter also referred to as “compound (P)”). It is preferable to have an epoxy group-containing polymer having a weight average molecular weight in the range of 10,000 to 500,000.

Of these, the thermosetting resin component preferably contains both the epoxy resin (A1-a) and the epoxy group-containing copolymer (A1-b). (A1-a) Epoxy resin As the epoxy resin (A1-a), 2 per molecule is used.
It is preferable to have at least two epoxy groups, for example, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, alicyclic epoxy resin, etc. No.

Of these epoxy resins, room temperature (25
° C) to 200 ° C for 1 minute to 2 hours.
It is preferable that the resin be cured by heating for 4 hours.
10 minutes to 12 hours at a heating temperature in the range of
It is more preferable that the resin be cured by heating for a long time. By heating and curing under such conditions, productivity is improved, and the influence of heating on the printed wiring circuit board and the like is reduced.

The weight average molecular weight of the epoxy resin (A1-a) is preferably in the range of 300 to 5,000, more preferably in the range of 400 to 2,000. When the weight average molecular weight is in such a range, the balance between the mechanical strength of the composition for forming a dielectric after heat curing and the productivity can be further improved. If the weight average molecular weight of the epoxy resin is less than 300, the mechanical strength after heat curing may be poor. On the other hand, when the weight average molecular weight exceeds 5,000, it takes a long time to uniformly dissolve the composition for forming the dielectric material, and the productivity may be poor.

The amount of the epoxy resin (A1-a) is from 1 to 20 parts by weight based on 100 parts by weight of the dielectric composite particles.
The value is preferably in the range of parts by weight, more preferably in the range of 5 to 15 parts by weight. If the amount of the epoxy resin (A1-a) is less than 1 part by weight, the mechanical strength of the composition for forming a dielectric after heat curing may be insufficient, and the amount of the epoxy resin (A1-a) may be insufficient. Exceeds 20 parts by weight (the decrease in the dielectric constant of the dielectric-forming composition may be large.) (A1-b) Epoxy group-containing polymer The epoxy group-containing polymer (A1-b) Is not particularly limited as long as it is a polymer having a specific weight average molecular weight having a unit derived from the compound (P) having an ethylenic double bond and an epoxy group in one molecule.

Such an epoxy group-containing polymer (A1-
Preferably, b) is a homopolymer of the compound (P) or a copolymer of the compound (P) and a monomer other than the compound (P). As the compound (P),
For example, epoxy group-containing (meth) acrylates or epoxy group-containing vinyl compounds may be used.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate and α-
Glycidyl ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl ( (Meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, and the like.

Examples of the epoxy group-containing vinyl compound include allyl glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether,
-Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinylcyclohexene oxide and the like. These can be used alone or in combination of two or more.

Among these epoxy group-containing monomers, glycidyl (meth) acrylate and glycidyl α-ethyl (meth) acrylate are particularly preferred. The structural unit derived from the compound (P) as described above is present in the epoxy group-containing polymer (A1-b) in an amount of preferably 10 to 100% by weight, more preferably 20 to 100% by weight. Is desirable.

When the content of the structural unit derived from the compound (P) is less than 10% by weight, the reactivity with the thermosetting resin may be significantly reduced. Further, as the epoxy group-containing polymer (A1-b), a compound (P), a vinyl group-containing compound containing no epoxy group other than the compound (P), a (meth) acrylamide compound, and a (meth) acrylate ester A homopolymer or a copolymer of two or more kinds of such monomers can also be used.

Examples of such a vinyl group-containing compound that does not contain an epoxy group include hydroxystyrene, isopropenylphenol, styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and p-methylstyrene.
Examples include methoxystyrene, vinylpyrrolidone, vinylcaprolactam, acrylonitrile, methacrylonitrile and the like.

As the (meth) acrylamide compound,
For example, acrylamide, methacrylamide, N, N
-Dimethylacrylamide and the like. further,
Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, Examples include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate.

Of these, styrene, acrylonitrile, hydroxystyrene, methyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferred. The weight average molecular weight of the epoxy group-containing polymer (A1-b) is preferably in the range of 10,000 to 500,000, more preferably 20,000.
00 to 400,000, particularly preferably 30,000 to
Desirably, the value is in the range of 300,000. When the weight average molecular weight of the epoxy group-containing polymer (A1-b) is in such a range, the balance between the sagging prevention during heating and the applicability of the composition for forming a dielectric becomes better.

When the weight-average molecular weight of the epoxy group-containing polymer (A1-b) is less than 10,000, the viscosity at the time of heat curing is rapidly reduced, and sufficient dripping prevention is not obtained. May have poor strength. On the other hand, if the weight average molecular weight exceeds 500,000, the viscosity of the composition for forming a dielectric substance may excessively increase, and the coatability may decrease.

The method for producing the epoxy group-containing polymer (A1-b) is not particularly limited.
It can be obtained by adding a radical generator and radically polymerizing the compound (P) and, if necessary, the other monomer. Such radical generators include, for example, diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds, persulfates alone or in combination of two or more. They can be used in combination. More specifically, for example, benzoyl peroxide, lauryl peroxide, 2,2'-azobisisobutyronitrilo, 4,4'-azobis (4-cyanovaleric acid) and the like can be mentioned.

It is also preferable to use an inorganic reducing agent such as sodium hydrogen sulfite and sodium pyrosulfite, and an organic reducing agent such as cobalt naphthenate and dimethylaniline, if necessary. By using such a combination, the radical reaction can be performed in a shorter time. Further, the iodine-containing fluorine compound may be used alone or in combination with the organic peroxide, azo compound or persulfate.

The amount of the radical generator is, for example, based on 100 parts by weight of the monomer containing the compound (P).
The value is preferably in the range of 0.1 to 10 parts by weight. It is also preferable to add a chain transfer agent when producing the epoxy group-containing polymer (A1-b). The use of the chain transfer agent makes it easier to adjust the weight average molecular weight of the epoxy group-containing polymer (A1-b).

Examples of such a chain transfer agent include halogenated hydrocarbons such as carbon tetrachloride, chloroform, and carbon tetrabromide, n-hexyl mercaptan, and n-hexyl mercaptan.
-Octyl mercaptan, n-dodecyl mercaptan,
t-dodecyl mercaptan, thioglycols, mercaptans such as thiopropionic acid, etc.
-Methylstyrene dimer and the like.

The radical polymerization is preferably performed in a solvent such as an aprotic polar solvent such as dioxane and THF, an ester such as ethyl acetate, and a ketone such as methyl ethyl ketone. The amount of the epoxy group-containing polymer (A1-b) is, for example, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the composite particles for a dielectric. Desirably a value. When the amount of addition is in such a range, it is possible to prevent the sagging during the heat curing of the composition for forming a dielectric and to achieve a better balance between the dielectric properties.

If the amount of the epoxy group-containing polymer (A1-b) is less than 1 part by weight, the composition for forming a dielectric may not have the effect of preventing sagging during heat curing. On the other hand, when the amount of the epoxy group-containing polymer (A1-b) exceeds 15 parts by weight, the ratio of the composite particles for a dielectric decreases relatively, and the dielectric property of the obtained dielectric decreases. There are cases. (A2) Resin component (thermoplastic type) Examples of the thermoplastic type resin component (A2) include (meth) acrylic resin, hydroxystyrene resin, novolak resin, polyester resin and the like. Among them, an acrylic resin such as a copolymer of the following monomer (M1) and monomer (M2) can be preferably used.

Examples of the monomer (M1) include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, and cinnamic acid. 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, (meth)
Examples include hydroxyl group-containing monomers such as 3-hydroxypropyl acrylate; and phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

Examples of the monomer (M2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentane. Monomers such as nil (meth) acrylate (M
(Meth) acrylic esters other than 1); styrene,
aromatic vinyl monomers such as α-methylstyrene;
Monomers that can be copolymerized with the monomer (M1) represented by conjugated dienes such as butadiene and isoprene can be exemplified.

The weight average molecular weight of the resin component (A2) is 1
It is preferably in the range of 000 to 1,000,000, more preferably 20,000 to 500,000.
00, particularly preferably in the range of 30,000 to 300,000. When the weight-average molecular weight is in such a range, for example, when the composition for forming a dielectric material of the present invention is used as a paste, prevention of dripping after printing of the dielectric paste and better balance between applicability and the like. Can be.

The weight average molecular weight of the resin component (A2) is 1
If it is less than 000, sufficient dripping prevention may not be obtained after printing the dielectric paste. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity of the composition for forming a dielectric may increase excessively, and the coatability may decrease. Although the method for producing the resin component (A2) is not particularly limited, the epoxy group-containing polymer (A1
It can be obtained by polymerizing the above monomer using the same radical generator or chain transfer agent as in -b).

The amount of the resin component (A2) to be added is, for example, 1 to 30 parts by weight based on 100 parts by weight of the dielectric composite particles.
The value is preferably in the range of parts by weight, more preferably in the range of 2 to 15 parts by weight. When the amount is in such a range, for example, the balance between the printability of the dielectric paste and the dielectric properties can be improved.

If the amount of the resin component (A2) is less than 1 part by weight, for example, the dielectric paste may not be applied uniformly. On the other hand, when the addition amount of the resin component (A2) exceeds 30 parts by weight, an organic residue may be generated when the resin component is heated and fired, and the dielectric property may be reduced. (2) The resin component used in the aqueous dispersion for electrodeposition (resin component (2)) When the dielectric composition according to the present invention is used by being contained in the aqueous dispersion for electrodeposition, the resin component (2) And one or more selected from polyimide resin, epoxy resin, acrylic resin, polyester resin, fluorine resin and silicon resin. Further, other components may be further contained in addition to these resins. Further, these resins may be chemically bonded to each other or to other components.

When such a resin component is used in the aqueous dispersion for electrodeposition, the resin component is preferably organic particles in the form of particles. The surface of the organic particles, which is a resin component comprising at least one of a polymerizable compound and a polymer, preferably has a charge in order to enable electrodeposition, and the surface charge may be anionic or cationic. In order to prevent electrode oxidation at the time of attachment, it is preferable to use a cationic type.

Among them, in the present invention, organic particles having a polyimide resin as a main component are used because a high dielectric constant film having excellent mechanical properties, chemical properties and electrical properties can be formed by electrodeposition. Is particularly preferred. As described above, the “polyimide resin” includes, for example, a precursor polymer (for example, polyamic acid or the like) curable by heating after electrodeposition, a monomer used for forming the polyimide resin, Oligomers, copolymer resins of monomers and other monomers used in the formation of polyimide resins or their precursor polymers, and also reactants of polyimide resins or their precursor polymers with other compounds and the like Means to include.

Filler The dielectric-forming composition of the present invention can further contain a filler in addition to the dielectric composite particles and the resin component. As such a filler, as an additive for improving the dielectric constant, acetylene black, carbon fine powder such as Ketjen black, conductive fine particles such as graphite fine powder,
Semiconductor fine particles such as silicon carbide fine powder are exemplified. When these fillers for improving the dielectric constant are added, the amount is preferably 0 to 10% by weight, more preferably 0.5 to 10% by weight, particularly preferably 1 to 5% by weight, based on the composite particles for a dielectric. It is desirable to use% amounts.

Other Additives The composition for forming a dielectric according to the present invention further comprises, as compounds other than the above, a curing agent, a glass powder, a coupling agent, a polymer additive, a reactive diluent, a polymerization inhibitor, Polymerization initiation aid, leveling agent, wetting improver, surfactant, plasticizer, ultraviolet absorber, antioxidant, antistatic agent, inorganic filler, antifungal agent, humidity control agent, dye dissolving agent, buffer solution , A chelating agent, a flame retardant, and the like. These additives can be used alone or in combination of two or more. (1) Curing agent When curing the resin component (A1), it is preferable to add a curing agent. The type of such a curing agent is not particularly limited, and examples thereof include amines, dicyandiamide, dibasic acid dihydrazide, and imidazoles as epoxy resin curing agents.

By adding such a curing agent,
The thermosetting of the epoxy resin can be performed efficiently. The amount of the curing agent is not particularly limited. For example, the amount of the curing agent is in the range of 1 to 30 parts by weight based on 100 parts by weight of the resin component (A1). Is preferred.

When the amount of the curing agent is less than 1 part by weight,
For example, the curability to an epoxy resin may be significantly reduced. On the other hand, if the amount of the curing agent exceeds 30 parts by weight, it becomes difficult to control the reactivity, and the storage stability of the epoxy resin may be reduced. When the thermosetting resin component (A1) is used, a curing accelerator can be used, if necessary. The type of such a curing accelerator is not particularly limited, and examples thereof include organic boron, tertiary amines, imidazole, and salts thereof. These are particularly preferred as curing accelerators for epoxy resins.

When such a curing accelerator is used, its amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin component. Is desirable. (2) Coupling agent The dielectric-forming composition of the present invention may contain a coupling agent. The addition of the coupling agent improves the applicability to a substrate such as a printed wiring board, and significantly improves the moisture resistance, so that excellent adhesion and the like can be obtained over a long period of time.

Examples of such a coupling agent include a silane coupling agent, an aluminum coupling agent,
At least one coupling agent selected from titanate-based coupling agents and zirconate-based coupling agents is included. Among these coupling agents, it is preferable to add a silane coupling agent since an excellent effect of improving moisture resistance and the like can be obtained by adding a relatively small amount.

The type of the silane coupling agent is not particularly limited, either.
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , N
-Decyltrimethoxysilane and the like. These can be used alone or in combination of two or more.

The amount of the coupling agent added is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the resin component (A).
It is desirable that the amount is in the range of 0.5 parts by weight, more preferably 0.5 to 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of addition may not be exhibited. On the other hand, when the addition amount exceeds 10 parts by weight, the coupling agent self-condenses, and the storage stability of the dielectric-forming composition may decrease.

[Dielectric Paste] The dielectric paste of the present invention contains a composition for forming a dielectric, and may contain an organic solvent if necessary. That is, the dielectric paste containing the dielectric-forming composition of the present invention can be used as it is when the dielectric-forming composition shows a paste. Further, if necessary, the resin component contained in the dielectric-forming composition can be dissolved in an organic solvent or the like, and the dielectric composite particles can be dispersed therein before use.

When the dielectric composition of the present invention is used as a dielectric paste, it is preferable to use the resin component (1). As the solvent, a known organic solvent can be used and is not particularly limited. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether And propylene glycol monomethyl -Propylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; Tolls; carbitol acetates such as ethyl carbitol acetate and butyl carbitol acetate; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate and acetic acid n-butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, Aliphatic carboxylic acid esters such as isobutyl lopionate; and others such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate Esters of toluene;
Aromatic hydrocarbons such as xylene; 2-heptanone, 3-
Ketones such as heptanone, 4-heptanone and cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone. . These solvents are preferably used alone or as a mixture of two or more. The amount of such an organic solvent used may be appropriately determined according to the type of the organic solvent and the like so that the viscosity of the obtained dielectric paste falls within the range described below, and is not limited. The amount is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight.

Such a dielectric paste comprises a dielectric composite particle, a resin component, and if necessary, a filler, an additive,
It can be prepared by uniformly mixing and stirring with an organic solvent using a mixer or the like. Examples of the mixer used for such mixing and stirring include a ball mill, a propeller mixer, a high shear mixer, a stirring and defoaming device, a three-roll, a V blender, a kneader, a microfluidizer, and the like.

Further, when mixing the materials constituting the dielectric paste, the temperature inside the mixer may increase. In that case, for example, using a cooling device or the like,
It is preferable to keep the temperature within ° C. If the temperature in the mixer exceeds 60 ° C., some of the resin components react and may be cured. The viscosity of the dielectric paste obtained by kneading and preparing such a composition is 1,000.
It is preferably adjusted to a value within the range of １，1,000,000 mPa · s (measuring temperature 25 ° C., the same applies hereinafter). If the viscosity of the dielectric paste is less than 1,000 mPa · s, the dielectric composite particles may be settled or may be easily dripped when applied. On the other hand, if the viscosity exceeds 1,000,000 mPa · s, it may be difficult to apply uniformly.

The viscosity of the dielectric paste is more preferably in the range of 10,000 to 600,000 mPa · s, and particularly preferably in the range of 30,000 to 400,000 mPa · s. When the viscosity is in such a range, the applicability of the dielectric paste and the dispersibility of the composite particles for the dielectric will be better. [Aqueous Dispersion for Electroplating] Aqueous Emulsion The aqueous dispersion for electrodeposition used in the present invention comprises the above-mentioned composition for forming a dielectric and an aqueous medium. Such an aqueous dispersion for electrodeposition is usually obtained by preparing an aqueous emulsion in which the organic particles of the resin component (2) are dispersed in an aqueous medium, and mixing this aqueous emulsion with the composite particles for a dielectric. Can be Therefore, the aqueous emulsion will be described first. In this specification, the term "aqueous medium" means a medium containing water, and the content of water in the aqueous medium is usually 1% by weight or more, preferably 5% by weight or more.

The aqueous emulsion may contain other media as necessary together with water. Other media used with water as needed include, for example, the polyamic acids, aprotic polar solvents used in the production of polyimides, esters, ketones, phenols, alcohols and the like. Hereinafter, an aqueous emulsion of organic particles mainly composed of a polyimide resin (hereinafter, referred to as "polyimide resin emulsion"), and an aqueous emulsion of organic particles mainly composed of an epoxy resin (hereinafter, referred to as "epoxy resin emulsion"). Aqueous emulsion of organic particles mainly composed of acrylic resin (hereinafter, referred to as "acrylic resin emulsion"), aqueous emulsion of organic particles mainly composed of polyester resin (hereinafter, referred to as "polyester resin emulsion"), mainly An aqueous emulsion of organic particles composed of a fluororesin (hereinafter, referred to as "fluorine resin emulsion") and an aqueous emulsion of organic particles composed mainly of a silicon resin (hereinafter, referred to as "emulsion").
It is called "silicone resin emulsion". ) Will be described. (I) Method for Producing Polyimide-Based Resin Emulsion When the organic particles used in the present invention are made of a polyimide-based resin, a polyimide-based high dielectric constant film having excellent mechanical properties, chemical properties and electrical properties is prepared. Can be formed. As a method for producing such a polyimide-based film by electrodeposition, the following two methods can be preferably used.

(B) an organic solvent-soluble polyimide,
(C) A method in which a polyimide resin emulsion containing organic particles composed of a hydrophilic polymer is used as an electrodeposition liquid, and the organic particles are electrodeposited. A method in which a polyimide resin emulsion containing organic particles composed of (D) a polyamic acid and (E) a hydrophobic compound is used as an electrodeposition liquid and the organic particles are electrodeposited, and the electrodeposited polyamic acid is dehydrated and closed by heating. .

As a method for producing a polyimide resin emulsion used in these methods, the above-mentioned method is described in JP-A-11-49951, and the above-mentioned method is described in JP-A-11-609.
The method described in JP-A-47-47 can be used. The method for producing the polyimide resin emulsion used in the above method will be described in more detail.

The method for synthesizing "(B) polyimide soluble in an organic solvent" is not particularly limited. For example, tetracarboxylic dianhydride and a diamine compound are mixed and polycondensed in an organic polar solvent. After obtaining a polyamic acid, a polyimide can be synthesized by subjecting the polyamic acid to a dehydration ring-closing reaction by a heat imidization method or a chemical imidization method. In addition, a polyimide having a block structure can be synthesized by performing polycondensation of a tetracarboxylic dianhydride and a diamine compound in multiple stages.

The organic solvent-soluble polyimide preferably has, for example, one or more reactive groups (a) such as a carboxyl group, an amino group, a hydroxyl group, a sulfonic acid group, an amide group, an epoxy group, and an isocyanate group. As a method for synthesizing a polyimide having a reactive group (a), for example, a reactive raw material such as a carboxylic acid dianhydride, a diamine compound, a carboxylic acid monoanhydride, or a monoamine compound used for the synthesis of polyamic acid may be used. Examples of the method include using a compound having the group (a) and leaving the reactive group (a) after the dehydration ring closure reaction.

The “(C) hydrophilic polymer” includes, as a hydrophilic group, an amino group, a carboxyl group, a hydroxyl group,
It has one or more sulfonic acid groups, amide groups and the like, and the solubility in water at 20 ° C. is usually 0.01 g / 100 g or more,
It is preferably composed of a hydrophilic polymer of 0.05 g / 100 g or more. In addition to the hydrophilic group, it is preferable to have at least one reactive group (b) capable of reacting with the reactive group (a) in the component (B). Such a reactive group (b)
As, for example, an epoxy group, an isocyanate group,
In addition to the carboxyl group, the same groups as the above-mentioned hydrophilic groups can be exemplified. Such a hydrophilic polymer is obtained by homopolymerizing or copolymerizing a monovinyl monomer having a hydrophilic group and / or a reactive group (b), or combining these monovinyl monomers with other monomers. It can be obtained by copolymerization.

This (B) polyimide soluble in an organic solvent and (C) a hydrophilic polymer are combined with a combination in which the reactive group (a) and the reactive group (b) in the hydrophilic polymer have appropriate reactivity. The polyimide and the hydrophilic polymer are mixed in a solution state, for example, in an organic solvent, and heated and reacted as necessary, and then the reaction solution is mixed with an aqueous medium. By mixing and removing at least a part of the organic solvent in some cases, the polyimide and the hydrophilic polymer are mutually bonded to obtain a polyimide resin emulsion composed of organic particles contained in the same particle. it can.

Next, the method for producing the polyimide resin emulsion used in the above method will be described in more detail. The method for synthesizing “(D) polyamic acid”, which is a precursor of polyimide, is not particularly limited. For example, a polyamic acid is prepared by a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound in an organic polar solvent. An acid can be obtained. In addition, a polyamic acid having a block structure can be synthesized by performing a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound in multiple stages. Note that a polyamic acid partially imidized by dehydrating and cyclizing the polyamic acid can also be used.

On the other hand, “(E) hydrophobic compound” is a compound having a group capable of reacting with at least an amic acid group in the polyamic acid (hereinafter referred to as “reactive group”). Examples of the reactive group include an epoxy group, an isocyanato group, a carbodiimide group, a hydroxyl group, a mercapto group, a halogen group, an alkylsulfonyl group, an arylsulfonyl group, a diazo group, and a carbonyl group. One or more of these reactive groups can be present in the hydrophobic compound. The term “hydrophobic” means that the solubility in water at 20 ° C. is generally less than 0.05 g / 100 g, preferably less than 0.01 / 100 g, and more preferably less than 0.005 g / 100 g. .

Examples of such a hydrophobic compound include epoxidized polybutadiene, bisphenol A type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, allyl glycidyl ether,
Glycidyl (meth) acrylate, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N,
N ', N',-tetraglycidyl-m-xylenediamine, tolylenediisocyanate, dicyclohexylcarbodiimide, polycarbodiimide, cholesterol, benzyl alcohol p-toluenesulfonic acid ester, ethyl chloroacetate, triazinetrithiol, diazomethane, diacetone (meth) One or more selected from acrylamide and the like can be used.

The polyamic acid (D) and the hydrophobic compound (E) are mixed and reacted in, for example, an organic solvent in a solution state, and the reaction solution is mixed with an aqueous medium. By removing at least a part of the solvent, it is possible to obtain a polyimide resin emulsion composed of organic particles containing a polyamic acid and a hydrophobic compound in the same particle.

The tetracarboxylic dianhydride used in the above method and the above method is not particularly limited. For example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9A
-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-
Aliphatic tetracarboxylic dianhydride such as 1,3-dione or alicyclic tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride And 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride and other aromatic tetracarboxylic dianhydrides. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

The diamine compound used in the above method is not particularly limited.
For example, aromatic diamines such as p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane; 1,1-metaxylylenediamine; Aliphatic diamines or alicyclic diamines such as 3-propanediamine, tetramethylenediamine, and 4,4'-methylenebis (cyclohexylamine); 2,3-diaminopyridine, 2,4-diamino-6-dimethylamino-1 , 3,
Has two primary amino groups and a nitrogen atom other than the primary amino groups in the molecule, such as 5-triazine, 2,4-diamino-5-phenylthiazole, bis (4-aminophenyl) phenylamine, etc. Diamines; mono-substituted phenylenediamines; diaminoorganosiloxane, and the like. These diamine compounds can be used alone or in combination of two or more. (Ii) Production method of epoxy resin emulsion The production method of the epoxy resin emulsion is not particularly limited, and a conventionally known method, for example, a method disclosed in
It can be produced by the methods described in JP-A-235495 and JP-A-9-208865. (iii) Method for Producing Acrylic Resin Emulsion The method for producing the acrylic resin emulsion is not particularly limited, but for example, it can be produced by a usual emulsion polymerization method. As the monomer, one or more kinds selected from general acrylic and / or methacrylic monomers may be used. At this time, in order to make the organic particles electrodepositable, a monomer having a cationic group such as an amino group, an amide group or a phosphono group, or a monomer having an anionic group such as a carboxyl group or a sulfonic acid group is used. The copolymer is preferably copolymerized, and the copolymerization amount is preferably from 5 to 80% by weight, more preferably from 10 to 50% by weight, based on the whole monomers used. As specific examples of the monomer having an amino group, dimethylaminoethyl acrylate, dimethylaminopropylacrylamide and the like can be preferably used. (Iv) Method for producing polyester-based resin emulsion The method for producing the polyester-based resin emulsion is not particularly limited, and conventionally known methods, for example, JP-A-57-10663 and JP-A-57-70153,
The method described in JP-A-58-174421 may be used. (V) Method for producing a fluorine-based resin emulsion The method for producing a fluorine-based resin emulsion is not particularly limited, and a conventionally known method, for example, JP-A-7-2
The method described in Japanese Patent No. 68163 may be used. (vi) Production method of silicone resin emulsion The production method of silicone resin emulsion is not particularly limited.
The method described in JP-A-60-60280 may be used. Aqueous dispersion for electrodeposition The aqueous dispersion for electrodeposition according to the present invention is obtained by dispersing the dielectric-forming composition in an aqueous medium as described above, and includes the resin component contained in the dielectric-forming composition. The organic particles enable electrodeposition. The meaning of the aqueous medium is the same as described above.

The volume ratio between the composite particles for dielectric and the organic particles contained in the aqueous dispersion for electrodeposition is preferably in the range of 5/95 to 80/20, and preferably in the range of 10/90 to 60/40. Is more preferred. The ratio of the composite particles for dielectric is 5
If it is less than the volume percentage, it is difficult to obtain a dielectric layer (film) having a high dielectric constant. On the other hand, when the proportion of the inorganic particles exceeds 80% by volume, the film-forming properties of the film become insufficient, which is not preferable.

The pH of the aqueous dispersion for electrodeposition is preferably 2
-10, more preferably 3-9, the solid concentration of the electrodeposition aqueous dispersion is preferably 1-50% by weight, more preferably 5-20% by weight, and the viscosity of the electrodeposition aqueous dispersion at 20 ° C is preferably Is preferably 1 to 100 mPa · s. When the pH, the solid content concentration or the viscosity is out of the above range, the dispersibility of the composite particles for dielectric or the organic particles is reduced, and the storage stability is insufficient, or the workability at the time of handling or use is reduced. There are cases.

Such an aqueous dispersion for electrodeposition is prepared by mixing an aqueous dispersion of the composite particles for a dielectric and an aqueous dispersion of the organic particles. The aqueous dispersion of the organic particles is mixed in the aqueous dispersion of the organic particles. It can be prepared by a method such as adding and mixing particles. It is preferable to use one of these methods. Further, before mixing with the aqueous dispersion of the organic particles, the pH of the aqueous dispersion of the composite particles for a dielectric is adjusted to include nitric acid, sulfuric acid, potassium hydroxide, or the like in order to improve the stability at the time of mixing. It is preferable to adjust the pH to 2 to 10 using the same.

The aqueous dispersion for electrodeposition according to the present invention can be stored at 20 ° C. for at least 5 days, more preferably at least 7 days, even more preferably at least 10 days without causing two-layer separation or significant change in viscosity. Above, particularly preferably 1
The storage stability can be 4 days or more. In addition, the aqueous dispersion for electrodeposition according to the present invention has the following general formula (1) in addition to the organic particles and the composite particles for a dielectric.

[0091]

Embedded image

(Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
8 represents a monovalent organic group, R ² represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenyl group, and n is an integer of 1 or 2. R ¹ and R ² may be the same or different. ), At least one selected from a hydrolyzate obtained by partially or entirely hydrolyzing a hydrolyzable group of the organosilane and a partial condensate obtained by partially dehydrating and condensing the hydrolyzate. One type (hereinafter, referred to as “organosilane condensate”) may be contained. A film formed from an aqueous dispersion for electrodeposition containing such an organosilane condensate, and the like, is obtained by crosslinking the organosilane condensate in the film, particularly when heat-cured after electrodeposition. Has excellent mechanical properties, chemical properties hardness and electrical properties.

In the general formula (1), R¹1-8 carbon atoms
As the organic group of, a linear or branched alkyl
Group, halogen-substituted alkyl group, vinyl group, phenyl
A 3,4-epoxycyclohexylethyl group, etc.
Can be mentioned. Note that R ¹Has a carbonyl group
May be. Note that R¹Is an alkyl group having 1 to 4 carbon atoms
Alternatively, it is preferably a phenyl group.

In the general formula (1), R ² has 1 to 5 carbon atoms.
As an alkyl group or an acyl group having 1 to 6 carbon atoms,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
Examples thereof include a tert-butyl group, an n-pentyl group, an acetyl group, a propionyl group, and a butyryl group. Note that R ²
Is preferably an alkyl group having 1 to 4 carbon atoms.

Examples of preferably used organosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, isobutyltrimethoxysilane and phenyltriethoxysilane. One of these organosilanes may be used alone, or two or more thereof may be used in combination. The “organosilane condensate” or the like preferably forms complex particles with the organic particles in the aqueous dispersion for electrodeposition of the present invention. The `` composite particles '' include those in which a compound constituting the organic particles and an organosilane condensate are chemically bonded, and those in which an organosilane condensate is adsorbed on the surface or inside of the organic particles. Point.

The amount of the organosilane condensate used is as follows:
The organic particles are preferably used in an amount of 0.1 to 100 parts by weight.
It is desirable that the amount be 1 to 500 parts by weight, more preferably 0.5 to 250 parts by weight. If the amount of the organosilane condensate is less than 0.1 part by weight, the desired effect may not be obtained. On the other hand, if it exceeds 500 parts by weight, the adhesiveness of the film tends to decrease.

Such composite particles can be produced by the following method or the like. Note that these methods may be combined. After the organosilane is added to the emulsion of the organic particles and at least a part of the organosilane is absorbed by the organic particles, a hydrolysis reaction and a condensation reaction of the organosilane are allowed to proceed.

The reaction for forming the organic particles is carried out in the presence of the organosilane condensate or the like dispersed in an aqueous medium. In order to allow the organosilane to be absorbed by the organic particles by the above method, a method of adding the organosilane to the emulsion and stirring the emulsion sufficiently may be used. At this time, it is preferable that the particles absorb 10% by weight or more (more preferably 30% by weight or more) of the added organosilane. The pH of the reaction system is usually adjusted to 4 to 10, preferably 5 to 10, and more preferably 6 to 8, in order to prevent the hydrolysis / condensation reaction of the organosilane from proceeding at an insufficient absorption stage. be able to. The treatment temperature for absorbing the organosilane into the organic particles is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 0 to 30 ° C. Processing time is usually 5-
It is 180 minutes, and preferably about 20 to 60 minutes.

The temperature at which the absorbed organosilane is hydrolyzed and condensed is usually at least 30 ° C., preferably at least 50 ° C.
To 100 ° C, more preferably 70 to 90 ° C, and the preferred polymerization time is 0.3 to 15 hours, more preferably 1 to
8 hours. Further, in the above method, the organosilane is mixed in an aqueous solution of a strongly acidic emulsifier such as an alkylbenzenesulfonic acid using a homomixer or an ultrasonic mixer, and the mixture is hydrolyzed and condensed to form an aqueous medium. Thus, an organosilane condensate and the like are obtained. In the presence of the organosilane condensate or the like, the organic particles may be formed preferably by emulsion polymerization.

[Dielectric, High Dielectric Film] The dielectric forming composition according to the present invention may be obtained as it is or by adding additives as needed and heating at a certain temperature or lower. Can be used for the production of dielectrics with high efficiency. Further, the composition for forming a dielectric material may be a high dielectric constant obtained by blending a conventionally known additive as needed with the dielectric paste or as the aqueous dispersion for electrodeposition and heating at a certain temperature or lower. Can be used for the production of a dielectric material. Also,
The shape of such a dielectric is not particularly limited depending on the application to be used, but the composition for forming a dielectric according to the present invention includes:
It is preferable to use it as a thin film of a high dielectric constant film. Method for Producing Dielectric or High Dielectric Constant Film The dielectric of the present invention comprises the dielectric composition of the present invention,
It can be obtained by heating at a temperature of 00 ° C or less, and the heating temperature is preferably 100 to 500 ° C, more preferably 1 to 500 ° C.
Desirably, the temperature is 50 to 300 ° C. Hereinafter, a method for producing a high dielectric constant film will be described in more detail. (1) When forming a high dielectric constant film using a dielectric paste To form a high dielectric constant film using a dielectric paste, for example, the dielectric paste is printed on a printed wiring board by a printing method such as screen printing. Or the like, and by heating in an oven or the like, the dielectric forming composition is cured or baked to obtain a film on which patterns of bumps and circuit boards are formed.

The thermosetting of the dielectric forming composition can be carried out using the thermosetting resin component (A1). When sintering the dielectric-forming composition by heating, it is preferable to use the resin component (A2). Such heating can be performed at a temperature of 500 ° C. or less, preferably 100 to 500 ° C., and more preferably 150 to 300 ° C. The heating time is preferably in the range of 1 minute to 24 hours, more preferably 10 minutes to 12 hours.

In the case of heating and curing or sintering the dielectric-forming composition, the heating method can be, for example, an oven, an infrared lamp, a hot plate or the like. (2) In the case of forming a high dielectric constant film using the aqueous dispersion for electrodeposition The aqueous dispersion for electrodeposition of the present invention may be used as it is, or may be diluted or concentrated. Can be appropriately blended and used for forming a high dielectric constant film. By a normal electrodeposition method using the electrodeposition aqueous dispersion, the dielectric composite particles and the organic particles in the electrodeposition aqueous dispersion can be electrodeposited on an electrode surface or the like to produce a high dielectric constant film. .

In producing the high dielectric constant film of the present invention, it is desirable to further heat and cure the resin component of the electrodeposited particles. The conditions for heat curing are 500 ° C. or less, preferably 100 to 500 ° C., more preferably 15 ° C.
It is desirable to carry out at 0 to 300 ° C. The heating time is preferably 5 minutes to 24 hours, more preferably 10 minutes to 12 hours.
It is desirable to perform within the time range. Physical properties of dielectric or high dielectric constant film A dielectric or high dielectric constant film obtained from the dielectric forming composition of the present invention has a dielectric constant of 30 or more, preferably 100 or more, more preferably 150 or more, Particularly preferably, it is 200 or more, and the dielectric loss tangent is 0.1 or less, preferably 0.08 or less, more preferably 0.08 or less.
It is desirably 6 or less. The lower limit of the dielectric loss tangent is not particularly limited.

The volume resistivity of such a dielectric or high dielectric constant film is preferably 10 ¹¹ Ω · cm or more.
More preferably, it can be 10 ¹² Ω · cm or more. The thickness of the high dielectric constant film is preferably 50 μm or less, more preferably 30 μm or less. The lower limit of the film thickness is not particularly limited, but is usually 1 μm or more.

[Electronic parts] The high dielectric constant film of the present invention can be obtained by heating and baking at a temperature of 500 ° C. or less, has a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less, and is a thin and static film. A capacitor or the like having a large capacitance can be formed. Further, electronic components such as a printed circuit board, a semiconductor package, a capacitor, and a high-frequency antenna provided with the high dielectric constant film can be small and have high density.

[0106]

According to the composite particles for a dielectric of the present invention,
As described above, a dielectric or a high dielectric constant film having a low dielectric tangent of 0.1 or less and a high dielectric constant of 30 or more can be formed at a low heating temperature of 500 ° C. or less. Further, since the high dielectric constant film of the present invention can be produced by screen printing or electrodeposition using a dielectric paste or an aqueous dispersion for electrodeposition, the film thickness can be controlled by adjusting printing conditions and electrodeposition conditions. It is easy, has excellent formability, and has excellent followability to substrates.

Further, a film having a high dielectric constant can be selectively formed by a film forming method using an electrodeposition liquid, and a high dielectric constant film can be formed at a lower cost and with higher precision than a photolithography or printing method. Since the high dielectric constant film of the present invention is a thin film and has a high dielectric constant, it is suitably used for electronic parts such as printed circuit boards, semiconductor packages, capacitors, and high frequency antennas.

Since the electronic component of the present invention has the high dielectric constant film, it can be reduced in size and thickness.

[0109]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

[0110]

Example 1 [Production of dielectric composite particles (1)] Barium titanate particles (trade name “HPAT-1”, manufactured by Fuji Titanium Co., Ltd., average particle diameter 0.6 μm, dielectric constant 200)
The composite particles (1) were obtained by depositing silver on the surface of barium titanate by silver vapor deposition in a vacuum of 0).

From the weight change before and after the deposition, it was found that 10% of silver had adhered to barium titanate. In addition, from SEM observation of the powder, it was confirmed that fine silver particles were attached to the particle surface.

[0112]

Example 2 [Production of dielectric composite particles (2)] Barium titanate particles (trade name “AT-02”, manufactured by Sakai Chemical Co., Ltd., average particle diameter 0.2 μm, dielectric constant 2000) 100
And 6 parts of Ketjen Black were preliminarily mixed, and a hybridizer (manufactured by Nara Machinery) was used to obtain dielectric composite particles (2) having Ketjen Black adhered to the surface of barium titanate by a mechanochemical method.

From the SEM observation of the obtained powder, it was confirmed that carbon fine particles had adhered to the particle surface. Further, it was confirmed by SIMS that 5% of carbon was attached to the barium titanate surface in terms of weight ratio.

[0114]

Example 3 Production of Composite Particles (3) for Dielectric Material Titanium oxide particles (trade name “TTO-55”, manufactured by Ishihara Sangyo Co., Ltd., average particle diameter 0.2 μm, dielectric constant 110) were electroless phosphorous -The surface was coated with nickel by a nickel plating method to obtain composite particles (3) for a dielectric.

From the SEM observation of the obtained powder, it was confirmed that nickel fine particles had adhered to the particle surface. Further, it was confirmed by SIMS that nickel adhered to the barium titanate surface in a weight ratio of 20%.

[0116]

Example 4 [Production of dielectric composite particles (4)] Barium titanate particles (trade name “HPAT-1”, manufactured by Fuji Titanium Co., Ltd., average particle diameter 0.6 μm, dielectric constant 200)
0) 100 parts and 10 parts of silver fine particles (manufactured by Vacuum Metallurgy Co., Ltd., average particle size: 0.05 μm) were preliminarily mixed, and silver was attached to the surface of barium titanate by a mechanochemical method using a hybridizer (manufactured by Nara Machinery). Thus, composite particles (4) for a dielectric were obtained.

From the SEM observation of the obtained powder, it was confirmed that fine silver particles adhered to the particle surface. Also, S
It was confirmed by IMS that 8% of silver was adhered to the barium titanate surface in terms of weight ratio.

[0118]

[Synthesis Example 1] [Preparation of polymer: production of thermosetting resin (epoxy group-containing polymer)] In a reaction vessel, 25 g of glycidyl methacrylate (abbreviated as GMA) and acrylonitrile (abbreviated as AN). 10), 15 g of methyl methacrylate (abbreviated as MMA) and 50 g of dioxane (abbreviated as DOX) were mixed to obtain a uniform reaction raw material solution.

The reaction solution was subjected to nitrogen bubbling for 30 minutes, followed by 2,2
1.9 g of azobisisobutyronitrile (abbreviated as AIAN) were added. The temperature inside the reaction vessel was raised to 70 ° C. while continuing nitrogen bubbling. The polymerization reaction was continued for 7 hours at the same temperature. The obtained reaction solution and a large amount of hexane were mixed to coagulate the polymer, and then the polymer was collected and redissolved in dioxane. The operation of coagulation with hexane and re-dissolving with dioxane was repeated five times to remove unreacted monomers.
Next, dioxane was scattered under the condition of 70 ° C. and reduced pressure,
A white epoxy group-containing polymer was obtained. The weight average molecular weight of this polymer was measured using GPC (gel permeation chromatography) and found to be 110,000.
Met.

[0120]

Synthesis Example 2 [Preparation of Organic Particle Emulsion: Polyimide Resin Emulsion] 32.29 g (90 mmol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride as tetracarboxylic dianhydride and 3.00 g of 1,3,3a, 4,5,9A-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione
(10 mmol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 3 as a diamine compound
6.95 g (90 mmol) and 2.49 g of organosiloxane LP7100 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
(10 mmol) was added to N-methyl-2-pyrrolidone 45
0 g and reacted at room temperature for 12 hours. afterwards,
32 g of pyridine and 71 g of acetic anhydride were added to the reaction solution.
Was added and a dehydration ring closure reaction was performed at 100 ° C. for 3 hours. Next, the reaction solution was distilled off under reduced pressure and purified to obtain a polyimide solution having a solid content of 10%.

A reaction vessel containing 100 parts of diethylene glycol monoethyl ether was placed under a nitrogen gas atmosphere at 85
C., and a mixture of 65 parts of n-butyl acrylate, 30 parts of dimethylaminoethyl acrylate, 5 parts of glycidyl methacrylate and 1 part of azobisisobutyronitrile was continuously added to the reaction vessel over 5 hours. While adding, solution polymerization was performed under stirring. After completion of the dropwise addition, stirring was further continued at 85 ° C. for 2 hours to complete the solution polymerization to obtain an acrylic polymer solution having a solid content of 50%.

50 parts (solid content) of a polyimide solution, 30 parts (solid content) of an acrylic polymer solution, and Epicoat 828
20 parts (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.)
After reacting at 70 ° C. for 3 hours, 3 parts of acetic acid was gradually added and mixed to adjust the pH. Then, distilled water 1000
Then, the mixture was vigorously stirred while gradually adding parts, thereby obtaining a cationic emulsion of organic particles containing a polyimide resin as a main component.

[0123]

[Synthesis Example 3] [Preparation of organic particle emulsion: epoxy resin emulsion] Tolylene diisocyanate and 2-
Blocked isocyanate composed of ethylhexanol 4
6.3 parts, 89.3 parts of an epoxyamine adduct obtained by reacting Epikote 828 (trade name, manufactured by Yuka Shell Epoxy Co.) with diethylamine were mixed, and 3.8 parts of acetic acid was used as a pH adjuster. Parts were added. This was poured into 1200 parts of ion-exchanged water with stirring to obtain a cationic emulsion of organic particles containing an epoxy resin precursor as a main component.

[0124]

Example 5 [Preparation of dielectric paste] 8 parts by weight of Epicoat 1004 (average molecular weight: 1600, manufactured by Yuka Shell Epoxy Co., Ltd.) which is an epoxy resin as a thermosetting resin,
And 3 parts by weight of the epoxy group-containing polymer obtained in Synthesis Example 1 was dissolved in 60 parts by weight of butyl cellosolve acetate to obtain a uniform resin solution. To this resin solution, 100 parts by weight of the dielectric composite particles (1) obtained in Example 1 and 8 parts of acetylene black were added. Then, using a three-roll mill, these dielectric paste composition materials
The mixture was kneaded for a time to obtain a dielectric paste. The viscosity of this dielectric paste was 50,000 mPa · s.

[0125]

Example 6 [Preparation of aqueous dispersion for electrodeposition] 15 parts by weight of the dielectric composite particles (1) obtained in Example 1, 0.2 parts by weight of acetylene black, and isopropyl alcohol 8
After mixing with 5 parts by weight using a homomixer, an ultrasonic dispersion treatment was performed to obtain a dispersion liquid (solid content: 15%) of the composite particles for a dielectric substance having no aggregate.

Further, an aqueous dispersion for electrodeposition was prepared by mixing 100 parts by weight of the dispersion with 40 parts of a cationic emulsion of organic particles containing the polyimide resin as a main component obtained in Synthesis Example 2.

[0127]

[Example 7] [Preparation of aqueous dispersion for electrodeposition] 15 parts by weight of the dielectric composite particles (4) obtained in Example 4 and 0.1 part by weight of acetylene black were added to isopropyl alcohol 8
After mixing with 5 parts by weight using a homomixer, an ultrasonic dispersion treatment was performed to obtain a dispersion liquid (solid content: 15%) of the composite particles for a dielectric substance having no aggregate.

Further, an aqueous dispersion for electrodeposition was prepared by mixing 100 parts by weight of the dispersion with 40 parts of a cationic emulsion of organic particles containing the polyimide resin as a main component obtained in Synthesis Example 2.

[0129]

Example 8 [Preparation of an aqueous dispersion for electrodeposition] 15 parts by weight of the dielectric composite particles (2) obtained in Example 2 and 0.1 part by weight of silicon carbide (average particle diameter: 0.1 μm) were added. After mixing with 85 parts by weight of isopropyl alcohol with a homomixer,
By performing an ultrasonic dispersion treatment, a dispersion liquid (solid content: 15%) of the composite particles for a dielectric substance without an aggregate was obtained.

Further, Synthesis Example 3 was added to 100 parts by weight of the dispersion.
20 parts of a cationic emulsion of organic particles containing an epoxy resin as a main component obtained in the above was mixed to prepare an aqueous dispersion for electrodeposition.

[0131]

Comparative Example 1 In Example 5, barium titanate particles (trade name “HPAT-1”, manufactured by Fuji Titanium Co., Ltd.) were used instead of the dielectric composite particles (1) obtained in Example 1.
A paste composition was obtained in exactly the same manner except that an average particle diameter of 0.6 μm and a dielectric constant of 2000) were used.

[0132]

Comparative Example 2 In Example 6, barium titanate particles (trade name “HPAT-1”, manufactured by Fuji Titanium Co., Ltd.) were used instead of the composite particles for dielectric material (1) obtained in Example 1.
An aqueous dispersion was prepared in exactly the same manner except that an average particle diameter of 0.6 μm and a dielectric constant of 2000) were used. Film Formation and Performance Evaluation Application by Screen Printing Method The dielectric pastes of Example 5 and Comparative Example 1 were printed on a copper foil with a screen printer. After pre-baking at 100 ° C. for 10 minutes, it was cured by heating in an oven at 150 ° C. for 30 minutes. When the film thickness was measured with an electromagnetic film thickness meter, a uniform coating of a dielectric film having a thickness of 20 μm was obtained. Coating by electrodeposition method In the aqueous dispersions for electrodeposition of Examples 6 to 8 and Comparative Example 2, a copper plate as a cathode and a SUS plate as a counter electrode were respectively disposed, and a copper plate on the cathode side by a constant voltage method of 100 V. The particles were electrodeposited on top. Thereafter, the mixture was heated at 100 ° C. for 10 minutes.
Example 8 was heated for 30 minutes at 150 ° C.
A 0 μm dielectric film was obtained.

The performances of the films produced through Examples 5 to 8 and Comparative Examples 1 and 2 were evaluated by the following methods. Table 1 shows the results. [Dielectric constant, dielectric loss tangent and volume resistivity] JIS K64
81.

The permittivity and the dielectric loss tangent are measured values at a frequency of 1 MHz. [Heat and moisture resistance (HAST test)]
A moist heat resistance test was performed for 72 hours under the conditions of 121 ° C., 100% humidity, and 2 atmospheres, and infrared spectroscopy was performed before and after the test.

・ ・ ・: No change and resistance is observed X: change is large and resistance is not observed

[0136]

[Table 1]

As can be seen from Table 1, all of the films obtained from Examples 5 to 8 had good electrical characteristics.
In Examples 6 and 7 using polyimide as the organic particles,
In particular, a film having a high volume resistivity was obtained. On the other hand, Comparative Examples 1 and 2 outside the range of the present invention were inferior in dielectric loss tangent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09C 3/08 C09D 5/44 Z C09D 5/44 H01B 3/12 303 H01B 3/12 303 304 304 H01G 4 / 20 H01G 4/20 C09D 5/00 Z // C09D 5/00 179/08 Z 179/08 C04B 35/00 Y F term (reference) 4G030 AA10 AA16 AA60 AA61 BA09 4J037 AA21 AA22 CA02 CA03 CC16 CC21 CC23 CC24 CC28 DD05 EE03 EE08 EE28 FF11 4J038 CD091 CG001 DB001 DD001 DJ021 HA216 KA08 KA15 MA08 MA10 NA17 PA04 5E082 FF05 FG06 5G303 AA10 AB06 AB07 BA04 BA08 BA12 CA01 CA09 CB03 CB35 CC01 DA01

Claims (21)

[Claims] An inorganic particle having a dielectric constant of 30 or more is partially or entirely coated with a conductive metal or a compound thereof, a conductive organic compound or a conductive inorganic substance. Composite particles for dielectrics. 2. The composite particles for a dielectric according to claim 1, wherein the inorganic particles are made of a titanium-based metal oxide. 3. The composite particle according to claim 2, wherein the titanium-based metal oxide is a double oxide. 4. An average particle diameter of the composite particles for a dielectric,
The composite particle for a dielectric according to any one of claims 1 to 3, wherein the particle size is 10 µm or less. 5. It is possible to form a dielectric having a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less by heating at a temperature of 500 ° C. or less. Part or the whole, a conductive metal or a compound thereof, a conductive organic compound or a conductive inorganic compound, and a composite particle for a dielectric, and a resin component comprising at least one of a polymerizable compound and a polymer. A composition for forming a dielectric, comprising: 6. The dielectric according to claim 5, wherein the dielectric obtained by heating the composition for forming a dielectric has a dielectric constant of 50 or more and a dielectric loss tangent of 0.1 or less. A composition for forming a dielectric. 7. The dielectric composition according to claim 5, wherein the inorganic particles are made of a titanium-based metal oxide. 8. The composition for forming a dielectric according to claim 7, wherein the titanium-based metal oxide is a titanium-based double oxide. 9. An average particle diameter of the dielectric composite particles,
The dielectric composition according to any one of claims 5 to 8, wherein the thickness is 10 µm or less. 10. A volume ratio of the dielectric composite particles and a resin component comprising at least one of the polymerizable compound and the polymer (volume of the dielectric composite particles / at least one of the polymerizable compound and the polymer). Volume of resin component)
Is 5/95 to 80/20, The composition for forming a dielectric according to any one of claims 5 to 9, wherein 11. The composition for forming a dielectric, further comprising:
The dielectric-forming composition according to any one of claims 5 to 10, further comprising a filler. 12. A dielectric paste containing the composition for forming a dielectric according to claim 5. Description: 13. The dielectric paste according to claim 12, wherein the resin component is a thermosetting resin that is a polymerizable compound, and the polymer is a thermoplastic resin. 14. An aqueous dispersion for electrodeposition comprising the dielectric-forming composition according to claim 5. Description: 15. The aqueous dispersion for electrodeposition according to claim 14, wherein the resin component comprising at least one of the polymerizable compound and the polymer is an electrodepositable organic particle. 16. The aqueous dispersion for electrodeposition according to claim 15, wherein the organic particles are made of a polyimide resin, and have a charge on the surface of the organic particles. 17. A high-dielectric-constant film formed by using the composition for forming a dielectric according to claim 5. Description: 18. A high dielectric constant film formed using the dielectric paste according to claim 12. 19. A high dielectric constant film formed by using the aqueous dispersion for electrodeposition according to claim 14. Description: 20. A dielectric composite in which a conductive metal or a compound thereof, a conductive organic compound or a conductive inorganic material is coated on a part or the entire surface of an inorganic particle having a dielectric constant of 30 or more. A composition containing particles and a resin component comprising at least one of a polymerizable compound and a polymer is heated at 500 ° C. or lower to obtain a dielectric having a dielectric constant of 30 or higher and a dielectric loss tangent of 0.1 or lower. A method for producing a dielectric, comprising: 21. An electronic component comprising the high dielectric constant film according to claim 17. Description: