TW201323502A - Resin composite material having high dielectric constant and method for producing same - Google Patents

Abstract

This resin composite material is formed from a resin composition that contains a resin and an insulated fine powder which is obtained by stirring a mixture that contains a conductive fine powder formed of a carbon material, an acid, a predetermined alkoxy metal composition and water and removing the solvent containing water by distillation. The resin composite material can have a reduced dielectric loss (tand), while maintaining a high dielectric constant. In addition, since a sol-gel reaction is caused to proceed under specific reaction conditions, decomposition of a resin does not occur even if the resin composite material is heated and melt-kneaded together with the resin. Furthermore, since this resin composite material uses a carbon material as a starting material of the insulated fine powder, the specific gravity of the resin composite material can be reduced to 2 or less.

Description

High dielectric constant resin composite material, and manufacturing method thereof

The present invention relates to a resin composite material characterized by a high dielectric constant and a method for producing the same.

One of the causes of IC (integrated circuit) data error is the influence of high frequency noise. In order to suppress this noise, a method of designing a capacitor having a large capacity on an interconnect substrate and removing high-frequency noise is known. Such a large capacity capacitor is realized to form a high dielectric layer on the interconnect substrate. Further, since the size of the built-in antenna or the thickness of the radio wave absorber is almost inversely proportional to the square root of the dielectric constant, the high dielectric constant material is useful for miniaturization and thinning of such members. In particular, it is desired to impart such characteristics to a resin material excellent in workability or formability.

As a high dielectric constant resin composite material, a ferroelectric material represented by barium titanate or the like has been proposed as a high dielectric constant filler system of 65 vol% or more, that is, a resin composite material filled with 80 wt% or more. (For example, refer to Patent Document 1). On the other hand, in the conductive powder, a high dielectric constant composition in which an insulating film is formed of a thermosetting resin (see, for example, Patent Document 2) is proposed, and since stable performance cannot be obtained, it is not commercially produced. In addition, in recent years, there has been proposed a method of coating a metal oxide in a metal powder (for example, refer to Patent Document 3), a method of coating a inorganic salt, and a coupling agent in a metal powder (for example, refer to Patent Document 4). The electric charge filler must also be high-filled, and because the metal powder is generally more The metal oxide has a higher specific gravity, so that the high dielectric constant resin composite material becomes heavier when it has a specific gravity of 3 or more.

Further, there has been proposed a method in which a single-layer carbon nanotube is wound into a polymer to be insulated and used for high dielectric constant of a resin material (for example, see Patent Document 5). However, this method involves a problem that, corresponding to the insulating film, since the wound polymer can be reversibly peeled off, stable performance cannot be obtained.

Therefore, the current state of the art is currently used in a manner in which a large amount of a filler is added as previously described. Therefore, in order to exchange for a high dielectric constant resin material, its intrinsic property is to sacrifice workability, formability, and lightness.

An insulating ultrafine powder in which a specific conductive ultrafine powder is coated with a specific metal oxide and a high dielectric constant resin composite material using the same are disclosed (for example, refer to Patent Documents 6 and 7). Forming the metal oxide of the insulating film of the insulating ultrafine powder, and dissolving the metal alkoxide as a metal hydroxide by sol-gel reaction in an organic solvent in which the conductive ultrafine powder is dispersed, and then performing dehydration condensation. It is obtained by performing surface treatment to make it hydrophobic.

The problem is to obtain the obtained insulating ultrafine powder in such a manner that the film obtained by the sol-gel method is porous, in particular, the dielectric constant of the high dielectric resin composite material which is highly filled with the insulating ultrafine powder. In addition to becoming higher, the tan δ indicating the loss of electric power tends to become large.

Further, in order to solve the above problems, (1) adding a liquid metal alkoxide to a methanol-containing organic solvent in which a specific conductive ultrafine powder is dispersed, and using an alcohol substitution reaction as a solid metal alkoxide, (2) Do this An insulating ultrafine powder having an insulating film obtained by entanglement of a conductive ultrafine powder as a precursor of an insulating film, followed by hydrolysis and dehydration polycondensation of the precursor, and a high dielectric resin composite material using the same (for example) Refer to Patent Document 8).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-237507

[Patent Document 2] Japanese Patent Laid-Open No. 54-115800

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-334612

[Patent Document 4] Japanese Patent No. 4019725

[Patent Document 5] Japanese Patent Publication No. 2004-506530

[Patent Document 6] International Publication Booklet WO2006/013947

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-94962

[Patent Document 8] Japanese Laid-Open Patent Publication No. 2011-49141

However, in the conventional insulating fine powder having an insulating film, when a metal alkoxide such as a titanium alkoxide which is highly reactive in a sol-gel reaction and which is relatively easy to form a film is used, the insulating fine powder and the resin are used. When melt-kneading is carried out, problems such as decomposition of the resin occur. Therefore, there arises a problem that a molded product cannot be obtained by melt molding by heating.

Further, the present invention provides an insulating layer which can reduce the dielectric loss tan δ while maintaining the dielectric constant of the resin composite material, and heat-melt and knead together with the resin without causing decomposition of the resin. A high dielectric ratio resin composite material of a fine powder and a method for producing the same are intended.

The inventors of the present invention have worked hard to solve the above problems, and by performing the sol-gel reaction of the metal alkoxide composition under the most suitable reaction conditions, the insulating micro-completed sol-gel reaction can be obtained by a simple method. The powder is used to find a resin composite material having a high dielectric constant which is heated and melt-kneaded with the resin and does not cause decomposition of the resin, and a method for producing the same. That is, the present invention is as follows.

[1] A resin composite material comprising a resin composition containing the following insulating fine powder and a resin, wherein the insulating fine powder contains a conductive fine powder made of a carbon material, an acid, a mixture of a metal alkoxide composition and water, obtained by distilling off a solvent containing water, wherein the content of the tetraalkoxydecane in the metal alkoxide composition is 15% by mass or more, and the titanium alkoxide The content is 10% by mass or less, and the volume ratio of the insulating fine powder to the resin is 5/95 to 50/50 (insulating fine powder/resin).

[2] A method for producing an insulating fine powder, characterized in that a mixture of a conductive fine powder made of a carbon material, an acid, an alkoxide metal composition, and water is mixed, and the solvent is distilled off. The content of the tetraalkoxydecane in the metal alkoxide composition is 15% by mass or more, and the content of the titanium alkoxide is 10% by mass or less.

[3] A method for producing a resin composite material, characterized in that the insulating fine powder obtained by the production method according to the above [2] is added to the resin to a volume ratio of the resin to the resin of 5/95 to 50/50 ( Insulating micropowder/resin).

According to the present invention, it is possible to provide a state in which the dielectric constant of the resin composite material is high while the dielectric loss tan δ is reduced, and the resin is decomposed and melted together with the resin. A high dielectric ratio resin composite of powder and a method of producing the same.

Further, since the resin composite material of the present invention is made of a carbon material on the raw material of the insulating fine powder, the specific gravity can be reduced to 2 or less.

[insulated fine powder]

The resin composite material of the present invention is characterized in that a conductive fine powder composed of a carbon material, an acid, an alkoxide metal composition, and a water mixture are stirred, and the insulating fine powder obtained by containing the water solvent is distilled off. And a resin composition containing a resin having a tetraalkoxydecane content of 15% by mass or more and a titanium alkoxide content of 10% by mass or less, and an insulating fine powder and The volume ratio of the resin is 5/95 to 50/50 (insulating fine powder/resin).

First, the insulating fine powder used for the resin composite material of the present invention will be described.

As the insulating fine powder of the resin composite material of the present invention, for example, a specific insulating fine powder obtained by the production method of the present invention can be used. That is, an insulating fine powder composed of a carbon material, an acid, an alkoxy metal composition, and water can be stirred and mixed by an insulating fine powder characterized by being used in the resin composite material of the present invention. And a solvent, and a method for producing an insulating fine powder having a tetraalkoxydecane content of 15% by mass or more and a content of titanium alkoxide of 10% by mass or less in the metal alkoxide composition The resulting fine powder.

As a conductive fine powder composed of the carbon material used in the present invention, as described in JP-A-2003-171562, the volume resistivity of the resin composite material is reduced when it is separately added to the resin material, that is, it is most suitable for use to impart conductivity. The effect of sex. Specifically, a fine powder of a conductive carbon material such as natural graphite, artificial graphite, furnace black, graphitized carbon black, carbon nanotube or carbon nanofiber is preferably used.

As a representative metal fine powder of a conductive material, since a part of the precious metal is easily oxidized, there is a disadvantage that the conductivity is liable to be lowered. Further, in the case where the metal atom is diffused from the fine powder, the insulating property of the resin composite material may be lowered. In this regard, in the present invention, it is preferable to use a conductive carbon material as the conductive fine powder, and there is no such problem, and further, the carbon material has a specific gravity of 2.2 or less, and has other conductive materials or a conventional high dielectric filler. There is no special feature, and there is also a lightweight effect of high dielectric ratio composite materials.

The conductive fine powder used in the present invention is preferably a particle diameter of 1 nm or more and 500 nm or less, more preferably 5 nm or more and 300 nm. Further, it is particularly preferably a spherical carbon material of 10 nm or more and 100 nm or less. Such a spherical carbon material, for example, carbon black, is obtained by thermally decomposing a hydrocarbon raw material in a gas phase. Further, the graphitized carbon black is vaporized by arc discharge in a reduced pressure vessel having an internal pressure of 2 to 19 Torr in a mixed gas atmosphere of He, CO, or the like, and is vaporized by arc discharge. The carbon vapor is obtained by cooling and solidifying.

In the present invention, the "spherical shape" does not necessarily have to be a strict spherical shape, and may be an isotropic shape. For example, it may have a polyhedral shape with a corner. The "particle diameter" in the case of non-spherical means the smallest diameter.

The above-mentioned conductive fine powder can be obtained as a commercial item as follows. For example, SEASTS or TalkerBlack #7100F manufactured by Tokai Carbon Co., Ltd., conductive carbon black #5500, #4500, #4400, #4300 or graphitized carbon black #3855, #3845, #3800, or Mitsubishi Chemical Corporation Commercial products such as Ketjen BlackEC and Ketjen Black EC600JD manufactured by #3050B, #3030B, #3230B, #3350B, MA7, MA8, MA11, or Lion Co., Ltd. are preferred.

In addition, as the conductive fine powder used in the present invention, a fibrous carbon material having a cross-sectional diameter of 1 nm or more and 500 nm or less, more preferably 5 nm or more and 300 nm or less, and still more preferably 10 nm or more and 200 nm or less is preferable. The length is preferably 3 times or more and 300 times or less of the cross-sectional diameter. Such a fibrous carbon material, for example, a carbon nanofiber or a carbon nanotube, is obtained by heating an organometallic compound of cobalt or iron as a catalyst and a hydrocarbon raw material by heating. Further, the carbon nanofiber system may be obtained by melt spinning a phenol resin and heating it in an inert atmosphere.

The term "fibrous" as used herein means a shape extending in the same direction, for example, an angular shape, a round bar shape, or a long spherical shape. Further, the so-called "cross-sectional diameter" in the case of an angular shape means a minimum diameter.

As described above, the fibrous electrically conductive fine powder can be obtained as follows. For example, VGCF manufactured by Showa Denko Co., Ltd., and VGNF, or Carbere manufactured by GSICreos Co., Ltd., and carbon nanofibers manufactured by Qunrong Chemical Industry Co., Ltd., are preferable.

Furthermore, the conductive fine powder used in the present invention is preferably a plate-shaped carbon material having a thickness of 1 nm or more and 500 nm or less, more preferably 5 nm or more and 300 nm or less, and still more preferably 10 nm or more and 200 nm or less. The length and the width are preferably 3 times or more and 300 times or less the thickness. Such a plate-shaped carbon material, for example, by purifying natural graphite or artificial graphite. Crush. Obtained by classification.

As the above-mentioned plate-shaped conductive fine powder, a commercially available product as follows can be obtained. For example, a SGP series manufactured by SEC Carbon Co., Ltd., a SNO series, or the like, or a scaly black lead powder manufactured by Nippon Black Lead Industries Co., Ltd., or a flaky black lead powder may be mentioned. Further, these may be further pulverized and subjected to precise classification. In addition, the term "plate shape" as used herein refers to a shape that is reduced in the same direction, for example, a flat spherical shape or a scale shape.

The conductive fine powder used in the present invention can be selected from the particle diameter, the cross-sectional diameter, and the thickness, and the conductivity can be prevented from being lowered depending on the quantum size effect. Moreover, manufacturing becomes easy to use in industry, and it is possible to suppress the decrease in operability depending on aggregation or the like. Further, the formation of the continuous layer is 50 vol% or more, that is, the resin property is not deteriorated at the addition rate. A continuous layer can be sufficiently formed within the range.

Further, when the shape of the conductive fine powder is fibrous or plate-shaped, the aspect ratio is preferably from 3 to 300. As the shape of the conductive fine powder used in the present invention, the fibrous shape is more preferable than the spherical shape or the plate shape. This is because it is a fibrous material, and it is sufficient that the amount of addition of the resin composite material having a dielectric constant of 20 or more in order to form a continuous layer is, for example, 30 vol% or less. Further, the particle diameter, the cross-sectional diameter, the thickness, and the aspect ratio can be obtained by a scanning electron microscope.

The metal alkoxide composition used in the present invention forms an insulating film on the surface of the conductive fine powder, and contains, as a means for cutting off conductivity, a tetraalkoxy decane of 15% by mass or more and a mass of alkoxide titanium 10 % below. It must contain a tetraalkoxynonane even if it does not contain titanium alkoxide. In other words, in the present invention, the metal alkoxide composition may contain a tetraalkoxynonane as a metal alkoxide, and may contain a composition of at least one of a metal alkoxide described later.

The alkoxide metal to be used in the invention may, for example, be an alkoxydecane, an alkoxy zirconium or an alkoxyaluminum, and an alkoxysilane or an alkoxy zirconium is preferred.

As the alkoxydecane, the alkoxy group in one molecule has four tetraalkoxydecanes as essential components in the present invention, and alkoxydecane other than tetraalkoxydecane, alkoxy group in one molecule There is no particular limitation on one or more, and it is preferred to use two or more alkoxy groups in one molecule, more preferably a trialkoxy decane having three alkoxy groups in one molecule.

As the alkoxy zirconium, if there is more than one alkoxy group in one molecule The alkoxy group in one molecule is preferably two or more, more preferably a trialkoxy zirconium having three alkoxy groups in one molecule, and having four alkoxy groups. The tetraalkoxy zirconium, and more preferably the tetraalkoxy zirconium.

These alkoxide metals also contain dimers, trimers, oligomers and the like.

In the present invention, since the specific dielectric constant and dielectric loss of the insulating film may be caused by the combination of the tetraalkoxy decane and the tetraalkoxy zirconium, the physical properties of the further melt viscosity or specific gravity become good as a whole.

Suitable examples of the tetraalkoxydecane include alkoxydecane such as tetramethoxynonane, tetraethoxysilane, tetrapropoxydecane, tetraisopropoxydecane or tetra-n-butoxydecane, and Its dimers, trimers, oligomers. In the present invention, these may be used singly or in combination of plural kinds.

The content of the tetraalkoxydecane in the metal alkoxide composition must be 15% by mass or more, preferably 15 to 100% by mass, more preferably 15 to 90% by mass, and particularly preferably 20 to 85% by mass. . When the content of the tetraalkoxydecane is within the above range, the balance between the specific dielectric constant and the dielectric loss of the resin composite material becomes good, and excellent dielectric properties can be obtained.

In addition, the amount of the tetraalkoxydecane used varies depending on the degree of the surface hydroxyl group of the conductive fine powder, and is preferably 0.01 to 200 parts by mass per 100 parts by mass of the conductive fine powder. Within this range, the obtained insulating fine powder can be sufficiently dispersed in the resin, and the adhesion between the insulating fine powder and the resin can be ensured. More preferably, it is 0.1 to 150 parts by mass, and particularly preferably 1 to 130 parts by mass. Also, when the tetraalkoxy zirconium described later is used in combination The total amount of the tetraalkoxydecane and the tetraalkoxyzirconium used may be within the above range.

Further, examples of the tetraalkyloxyzirconium include tetrapropoxy zirconium, tetraisopropoxy zirconium, tetra-n-butoxy zirconium, tetra-n-butoxy zirconium, and tetra-t-butoxy zirconium. Alkoxy zirconium, and its dimers, trimers, oligomers. As such a particularly preferable one, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetrapropoxy zirconium, and tetraisopropoxy zirconium are mentioned. In the present invention, these may be used singly or in combination of plural kinds.

a trialkoxy decane having three alkoxy groups in one molecule, wherein the alkoxy group is bonded to a ruthenium atom, and the organic group other than the alkoxy group is bonded to a ruthenium atom, and the molecule contains a group selected from More preferably, the group of the group consisting of a phenyl group, a vinyl group, an isobutyl group, a decyl group, a glycidoxy group, an amine group, a thiol group, and a methacryloxy group is preferably a group. Specifically, a known decane coupling agent or the like containing such a group in an organic group structure is preferable as the trialkoxy decane.

Suitable examples of the trialkoxydecane include methyltriethoxydecane, phenyltriethoxydecane, methyltrimethoxydecane, phenyltrimethoxydecane, isobutyltrimethoxydecane, and hydrazine. Trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, γ-aminopropyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-hydrogen sulphide Propyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, N-β(aminoethyl)-γ-aminopropyltrimethoxydecane, and dimers thereof, Terpolymers, oligomers, and the like. Among them, preferred are oligomers of methyltrimethoxydecane, oligomers of phenyltrimethoxydecane, and γ-epoxypropane An oligomer of oxypropyltrimethoxydecane, an oligomer of γ-aminopropyltriethoxydecane, an oligomer composed of methyltrimethoxydecane and phenyltrimethoxydecane, An oligomer composed of methyltrimethoxydecane and γ-glycidoxypropyltrimethoxydecane.

The trialkoxy decane is used in combination with a tetraalkoxy decane to form an insulating film to cut off the conductivity of the conductive fine powder, and to impart flexibility to the insulating film and affinity with the resin. By imparting softness and affinity with the resin, a strong stress is applied to the composite of the insulating fine powder and the resin material (for example, heat-melting and mixing with the thermoplastic resin under mass production conditions using a two-axis extruder or the like) Refining) suppresses the destruction of the insulating film and maintains dielectric properties.

In addition, the amount of use of the trialkoxy decane varies depending on the amount of surface hydroxyl groups, and is preferably 100 parts by mass or less based on 100 parts by mass of the conductive fine powder. If it is in this range, the insulating fine powder can be sufficiently dispersed in the resin, and the adhesion between the insulating fine powder and the resin can be ensured. More preferably, it is 0.1 to 70 parts by mass, and particularly preferably 1 to 50 parts by mass. Further, as described above, the alkoxy group in one molecule may be used in combination with one alkoxy metal or one alkoxy group in one molecule as two alkoxy groups.

In the present invention, the metal alkoxide composition may also contain titanium alkoxide. The titanium alkoxide is not particularly limited as long as it has one or more alkoxy groups in one molecule. More specifically, a titanium alkoxide is exemplified by adding a ruthenium atom of the above alkoxysilane to a titanium atom.

The content of the alkoxide titanium in the metal alkoxide composition must be 10% by mass or less, and it is preferable that titanium alkoxide is not contained. Previous sol-gel reaction, It is preferred to use a titanium alkoxide which has a high reactivity and is relatively easy to form a film. According to the present invention, titanium alkoxide such as titanium is not used, that is, even if it is inferior in reactivity with titanium alkoxide. Alkoxy decane such as decane or alkoxy zirconium or the like finally forms a good insulating film, which can be said to be a characteristic effect of the present invention. Further, in the present invention, even if a titanium alkoxide having high reactivity is used, the sol-gel reaction is stopped to obtain an insulating fine powder, and the resin, particularly chemical resistance, that is, heat-melting and kneading simultaneously with the easily hydrolyzable resin Does not cause decomposition of the resin. This point can also be said to be a characteristic effect of the present invention.

The acid used in the present invention may be any inorganic acid or organic acid. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, nitrous acid, perchloric acid, amine sulfonic acid, etc., and the organic acid may be used. Preferably, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluenesulfonic acid or the like is preferred. The catalytic effect is more preferably phosphoric acid, hydrochloric acid or acetic acid from the viewpoint of residualness after formation of the film.

The water used in the present invention is substantially water containing no impurities, and preferably ion-exchanged water, distilled water, pure water, ultrapure water or the like is exemplified.

In the present invention, the metal alkoxide composition is produced by the reaction of an acid and water in the system, so that it is not necessary to intentionally add an alcohol, thereby improving the dispersibility of the mixed solution and the conductive fine powder, and more uniformly in the system. It is preferred to advance the sol-gel reaction, add the produced alcohol, and further mix the alcohol. The alcohol to be further mixed is not particularly limited as long as it can be uniformly dissolved in water, and examples thereof include methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, and tert-butyl alcohol. good. It is also possible to use an organic solvent together with an alcohol as Examples of the organic solvent include acetone, 2-butanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, toluene, and xylene. It is better.

When an alcohol is used, the alcohol is preliminarily mixed with an acid and water, and is dissolved as an acidic aqueous solution containing an alcohol as a suitable aspect. The mass ratio of the alcohol in the acidic aqueous solution containing alcohol is preferably in the range of (water/alcohol) 3/97 to 100/0, and more preferably in the range of 5/95 to 99/1, particularly preferably 10/90~ 97/3.

The acidic aqueous solution containing alcohol is preferably pH 3 or higher, and the weak acidity at pH 7 is preferably insufficient. When pH7 or more and pH7 is not full, a part of the tetraalkoxy decane used as the metal alkoxide composition becomes a decyl alcohol state, and it is difficult to carry out a condensation reaction between stanols, and it becomes easy to be stable, and is electrically conductive. The functional group reaction on the fine powder becomes easier.

The concentration of the acid is defined by the inorganic acid of 0.0001 to 2, preferably 0.001 to 1, and the organic acid is 0.0001 to 10, preferably 0.001 to 5.

In the present invention, a method of mixing the conductive fine powder, the acid, the metal alkoxide composition, and water composed of the carbon material is not particularly limited. These may be mixed individually, or a part of the mixture may be pre-mixed and added with residual components. The addition rate may be all at once or may be added in several portions, and continuous dripping may be performed. The same is true when alcohol is further used.

In the present invention, in order to obtain an insulating fine powder, it is important to distill off the solvent from the mixture. By distilling off, a metal alkoxide composition such as tetraalkoxydecane is condensed by a sol-gel reaction to react with a functional group on the conductive fine powder. As a method of distilling off the solvent, heating or decompression may be used, or the same Heat and depressurize at the time.

The insulating fine particles obtained by distilling off the solvent may be further pulverized, and any of dry pulverization and wet pulverization may be used as the pulverization method. Examples of the industrial pulverizing apparatus include a hammer mill, a roller crusher, a ball mill, a pin mill, a jet mill, a homogenizer, an ultrasonic pulverizer, a disperser, and a colloid mill. Any one can be used.

Further, the insulating fine particles obtained by distilling off the solvent may be subjected to a baking treatment. The firing treatment is preferably carried out at a temperature ranging from 200 ° C to 1000 ° C for 30 minutes to 24 hours. However, since the conductive fine powder of the present invention is a carbon material, the firing environment is preferably non-oxidizing. That is, it is preferred to carry out nitrogen substitution or argon substitution to cut off oxygen.

[Resin composite material]

The resin composite material of the present invention, and the above-mentioned insulating fine powder and resin, are characterized by a volume ratio (insulating fine powder/resin) of 5/95 to 50/50. In other words, the resin composite material of the present invention is obtained by mixing the above-mentioned insulating fine powder in a range of 5 to 50 vol% in a resin.

The insulating micropowder is obtained by mixing 5 to 50 vol% of the resin to obtain a resin composite material having a dielectric constant of 7 or more, or a dielectric loss of tan δ of less than 0.1. More preferably, it is a resin composite material having a dielectric constant of 7 or less and less than 45, a dielectric loss tan δ of 0.003 or more and less than 0.1, and a specific gravity of 0.9 or more and 2 or less. When the amount of the insulating fine powder is less than 5 vol%, a continuous layer cannot be formed in the resin composition, and a sufficient specific dielectric ratio cannot be obtained, and finally, the specific dielectric constant is less than 7. On the other hand, when it is more than 50 vol%, the original processability and the like of the resin composition are lost. It does not impair the original processability or lightness of the resin material, because the high dielectric constant is found, and the amount of the insulating fine powder is 5 to 30 vol% (as the volume ratio (insulating fine powder/resin) is 5 /95~30/70) is better.

In order to achieve a high dielectric constant resin composite material having a dielectric loss of 7 or less and a dielectric loss tan δ of 0.003 or more and less than 0.1, the filler must be mixed by 50 vol% when using a conventional high dielectric filler. In the present invention, when the amount of the insulating fine powder is 5 to 50 vol%, a resin composition having a high dielectric constant can be obtained. Therefore, the resin composite material of the insulating fine powder of the present invention can be found without detracting from the original molding processability or lightness of the resin material, and a high dielectric constant can be found.

In the present invention, as the resin to which the above-described insulating fine powder is added, a thermoplastic resin, an elastomer, and a thermosetting resin are preferable, and a thermoplastic resin is more preferable.

Examples of the thermoplastic resin include general-purpose plastics such as polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyvinyl acetate, ABS resin, AS resin, and acryl resin; polyacetal, polyamine, Polycarbonate, modified polyphenylene ether, polybutylene terephthalate, etc. Plastic; polyarylate, polybenzazole, polyphenylene sulfide, polyether oxime, polyetheretherketone, polyimine resin, fluororesin, polyamidoximine, etc. engineering. Plastics are preferred. Among these, the mechanical strength, low dielectric tangent, and good injection are obtained. From the viewpoint of moldability, any of polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyphenylene sulfide, and polypropylene is suitable. Further, the resin is decomposed by heat-melting and kneading together with the resin of the present invention, and from the viewpoint of effectively utilizing the effects of the present invention, polycarbonate or polyparaphenyl having a property of easily decomposing the resin can be used. A combination of ethylene diformate and polybutylene terephthalate.

As the elastomer, for example, isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylonitrile-based elastomer, polyester-based elastomer, polyamine-based elastomer, or nucleus may be used. A thermoplastic elastomer of MBS, MAS or the like of a shell-type elastomer.

Examples of the thermosetting resin include a phenol resin; an amine resin such as a urea resin, a melamine resin, or a benzoguanamine resin; an unsaturated polyester resin; a diallyl phthalate resin; an alkyd resin; and an epoxy resin. A urethane resin such as a polyurethane or a hydrazine resin such as a fluorene polymer is preferable.

The high dielectric constant resin composite material of the present invention is preferably used in addition to a filler for the purpose of purifying a high dielectric constant. Examples of the filler include talc, mica, clay, ettringite, calcium carbonate, glass fiber, glass beads, glass balloons, ground fibers, glass cullet, carbon fiber, carbon flakes, carbon balls, carbon-milled fibers, Sheet metal, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass chip, cerium oxide, ceramic particle, ceramic fiber, Aramid particle, Aramid fiber, polyarylate Reinforcing agents such as fibers, graphite, conductive carbon black, and various whiskers (Whisker) are preferred.

Further, as other fillers, a halogen-based, phosphate-based, metal-salt, red phosphorus, metal water, and the like may be mixed; a thermal stabilizer; an ultraviolet absorber; a light stabilizer; Lubricant; a pulverizing agent such as PTFE particles; a coloring agent such as a pigment or a dye such as titanium oxide; a crosslinked particle of acrylonitrile, a crosslinked particle of a ruthenium oxide polymer, an extremely thin glass shard, and a calcium carbonate particle. Diffusion agent; fluorescent brightener; phosphorescent pigment; fluorescent dye; antistatic agent; flow modifier; nucleating agent; inorganic and organic antibacterial agent; photocatalyst antifouling agent for microparticle titanium oxide, micronized zinc oxide, etc. An impact modifier represented by a graft rubber; an infrared absorbing agent; a photochromic agent or the like is preferred.

The method for producing the resin composite material of the present invention is not particularly limited, and is preferably a method for producing the resin composite material of the present invention, that is, an insulating fine powder obtained by the above-described production method, which can be characterized by It is produced by mixing a manufacturing method as a resin having a volume ratio of the above-mentioned resin of 5/95 to 50/50 (insulating fine powder/resin).

More specifically, the resin composite material of the present invention, the above-mentioned quantitatively-insulated fine powder, resin, and if necessary, are preferably mixed with various additives, and kneading can be produced by a known method. In the above, a thermoplastic resin is used as the resin, and the melted kneading method is performed by mixing the insulating fine powder in the melt of the thermoplastic resin, or dispersing the insulating fine powder in a solution in which the thermoplastic resin is dissolved in a solvent. A method of removing a suitable solvent or the like is employed as a production method suitably employed.

Here, mixing or kneading, usually used, for example, using a ribbon mixer, Henschel mixer, Banbu A method of a Banbury mixer, a Drum tumbler, a single screw extruder, a twin screw extruder, a Konida mixer, a multi-axis screw extruder, or the like is preferred.

The heating temperature during kneading is usually selected in the range of 220 to 350 °C.

Therefore, the obtained resin composite material can be applied to various known molding methods, for example, injection molding, hollow molding, extrusion molding, compression molding, calender molding, rotational molding, etc., and can be provided in the electrical field or the electronic field as the first A molded article having a high dielectric constant, and various molded articles are produced.

When the resin composite material of the present invention is used as a radio wave absorbing material, a magnetic metal powder having a ferrite powder or iron as a main component or a conductive powder of a carbon-based or tin oxide-based conductive powder can be used to adjust the radio wave absorption property. Further, as the filler, expanded black lead powder or the like having a conductive powder as a flame retardant effect may be further added.

When the resin composite material of the present invention is used for an antenna substrate, the resin composite material preferably has a dielectric constant of 7 or more and less than 45, and a dielectric loss tan δ of 0.003 or more and less than 0.1. Then, such a high dielectric constant resin composite material is a layer having a thickness of 1 μm or more and 3 mm or less, more specifically, a film formed on a thickness of 1 μm to 300 μm or at least one side of a sheet formed on a thickness of 300 μm to 3 mm. A wiring pattern is provided on the surface to form an antenna substrate.

Further, if necessary, a through hole may be formed in the film or sheet of the resin composite material.

When the resin composite material of the present invention is used on a non-contact IC card/tag, the wiring pattern of the IC on the antenna substrate can be directly wired to make the IC card embedded therein. The / tag is in contact with the antenna substrate and can also be used as a booster antenna. Moreover, when a film or a sheet of a resin composite material is used as an antenna substrate or a non-contact IC card, a protective film or the like may be attached if necessary.

When the resin composite material of the present invention is used for the above-mentioned radio wave absorber, a radio wave absorber having a specific dielectric constant of 7 or more is obtained. In order to realize a radio wave absorber having a dielectric constant of 7 or more, when a conventional high dielectric filler is used, the filler must be mixed at a level of 50 vol% or more. However, when the insulating fine powder obtained by the present invention is used, the insulating fine powder can be obtained by mixing 50 vol% or less, that is, a smaller amount of the resin of the conventional high dielectric filler. can be realised. Therefore, the resin composite material in which the insulating fine powder obtained by the present invention is mixed does not impair the molding processability or lightness which is originally a resin material, and exhibits a high dielectric constant.

The radio wave absorber of the resin composite material of the present invention has a high dielectric constant, and when thinned, the thickness of the wavelength of the absorbed electric wave can be changed to 1/20 or less. Further, the radio wave absorbing material using the resin composite material of the present invention can be used inside the casing to exhibit excellent performance as an electronic device. Further, since the carbon material is used for the raw material of the insulating fine powder, the specific gravity of the radio wave absorber can be reduced to 2 or less, and further weight reduction can be achieved.

[Examples]

Next, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

The measurement of the melt viscosity, the specific dielectric constant (ε r), the dielectric loss (tan δ ), and the specific gravity of the resin composite material obtained in each of the examples and the comparative examples was carried out by the following method.

The melt viscosity was measured as MVR (Mass volume rate) by a melt index (F-F01, manufactured by Toyo Seiki Seisakusho Co., Ltd.).

For the determination of specific dielectric ratio (ε r) and dielectric loss (tan δ ), the resin composite was molded at 30 mm. On a magnetic disk having a thickness of 3 mm, an impedance analyzer (4294A, manufactured by Agilent Co., Ltd.) was used to measure at room temperature at 1 MHz.

Further, the weight of the formed magnetic disk was measured for the measurement of the specific gravity, and was determined by measuring the volume in water at 23 °C.

(Synthesis Example 1 of Insulating Micropowder)

Using a 5 L stainless steel container with a jacket, 180 g of ion-exchanged water, 5 g of 0.5 mol/l phosphoric acid reagent, 40 g of tetraethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04), and 20 g of alkoxy group Metal (manufactured by Shin-Etsu Chemical Co., Ltd., a mixed solution of KR-510 (an oligomer composed of methyltrimethoxydecane and phenyltrimethoxydecane)) was put into 100 g of carbon black (spheroid particles) In a diameter of 5 to 100 nm and an average particle diameter of 40 nm, the mixture was stirred at room temperature for 1 hour. Thereafter, 0.5 MPa of steam was introduced into the jacket, and the mixture was further stirred under a reduced pressure for 30 minutes to raise the temperature to 100 ° C, and the solvent was distilled off to synthesize the insulating fine powder. The insulating fine powder was observed through a scanning transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.) to form an SiO ₂ film on the surface of the carbon black.

(Synthesis Example 2 of Insulating Micropowder)

An alcoholic acidic aqueous solution (pH 4) containing 50 g of methanol, 130 g of ion-exchanged water, and 5 g of a 0.5 mol/l phosphoric acid reagent was prepared. A mixed solution of a full amount of an alcoholic acidic aqueous solution and 70 g of tetraethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) was placed in 100 g of carbon black (spheroid particles) using a 5 L stainless steel container with a jacket. In a diameter of 5 to 100 nm and an average particle diameter of 40 nm, the mixture was stirred at room temperature for 1 hour. Thereafter, 0.5 MPa of steam was introduced into the jacket, and the mixture was further stirred under a slight reduced pressure for 30 minutes to raise the temperature to 100 ° C, and the solvent was distilled off to synthesize the insulating fine powder. The SiO ₂ film was formed on the surface of the carbon black by observation of the insulating fine powder by a scanning transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.).

(Synthesis Example 3 of Insulating Micropowder)

An alcohol-containing acidic aqueous solution similar to that used in Synthesis Example 2 of the insulating fine powder, 40 g of tetraethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04), and 20 g were used in a 5 L stainless steel container with a jacket. A metal alkoxide (manufactured by Shin-Etsu Chemical Co., Ltd., KR-510 (an oligomer composed of methyltrimethoxynonane and phenyltrimethoxydecane)) was put into 100 g of carbon black (ball) The particles having a diameter of 5 to 100 nm and an average particle diameter of 40 nm were stirred and mixed at normal temperature for 1 hour. After that, 0.5 MPa of steam was introduced into the jacket, and 30 minutes under micro-decompression. The bell was further stirred while the temperature was raised to 100 ° C, and the solvent was distilled off to synthesize the insulating fine powder.

First, the use of carbon black as a raw material was observed by a scanning transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.) at a magnification of 3 million times, and the surface was subjected to energy dispersive X-ray spectrometry (Japan Electronics Co., Ltd.) UTW type Si (Li) semiconductor detector). As a result, Si/C was 0 in one portion of the photograph, and since Si was not present, it was confirmed that the SiO ₂ film was not present (see Fig. 2).

Then, the obtained insulating fine powder was observed by a scanning transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.) at a magnification of 3 million times, and it was confirmed that an SiO ₂ film was formed on the surface of the carbon black. In addition, in order to investigate the composition of the SiO ₂ film on the surface of the insulating fine powder and perform energy dispersive X-ray spectrum measurement (UTW type Si (Li) semiconductor detector manufactured by JEOL Ltd.), the surface 1 and In the case of part 3, the Si/C is higher than the center portion 2, and it is confirmed that Si on the surface is localized. Here, the surface 1-3 is shown in the part of the scanning electron micrograph of the insulating fine powder obtained by this synthesis example 3. FIG.

Further, in order to measure the powder resistance of the insulating fine powder, the powder resistance measuring system (the MCP-PD51 Roresuta PA system four-terminal four-probe method JIS K7194 standard manufactured by Mitsubishi Chemical Analytic Co., Ltd.) was measured and pressurized at 38.2 MPa. The volume resistivity of the next 2.9mm thick is 0.10 Ω. Cm. Further, the volume resistivity of the raw material carbon black under a pressure of 38.2 MPa of 3.0 mm is 0.031 Ω. Cm because of the invention The resistance value of the powder itself is increased, and the insulating film is formed.

(Synthesis Example 4 of Insulating Micropowder)

40 g of tetraethoxy decane of Synthesis Example 3 and 20 g of alkoxy metal (KR-510, manufactured by Shin-Etsu Chemical Co., Ltd.) were used instead of the insulating fine powder, and 110 g of tetraethoxy decane and 30 g of alkoxy group were used. The metal (KR-510, manufactured by Shin-Etsu Chemical Co., Ltd.) was synthesized in the same manner as in Synthesis Example 3 of the insulating fine powder to synthesize the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 5 of Insulating Micropowder)

20 g of alkoxy metal (KR-510, manufactured by Shin-Etsu Chemical Co., Ltd.) in the synthesis example 3 of the insulating fine powder was replaced with 20 g of alkoxy metal (manufactured by Shin-Etsu Chemical Co., Ltd., KC-89S (A) The oligomer of the methoxymethoxysilane ()) was synthesized in the same manner as in Synthesis Example 3 of the insulating fine powder to synthesize the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 6 of Insulating Micropowder)

20 g of alkoxy metal (KR-510, manufactured by Shin-Etsu Chemical Co., Ltd.) in the synthesis example 3 of the insulating fine powder was replaced with 20 g of alkoxy metal (manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1056). (Oligomer composed of methyltrimethoxydecane and γ-glycidoxypropyltrimethoxydecane)) The insulating powder was synthesized in the same manner as in Synthesis Example 3 of the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 7 of Insulating Micropowder)

In addition to 70 g of tetraethoxy decane of Synthesis Example 2 of the insulating fine powder, 150 g of a solution of tetrapropoxy zirconium in 1-propanol (Organics ZA-45, tetrapropoxyl, manufactured by Matsumoto Fine Chemical Co., Ltd.) was used in combination. Zirconium 75 mass% solution) was synthesized in the same manner as in Synthesis Example 2 of the insulating fine powder to synthesize the insulating fine powder. In the same manner as in Synthesis Example 2 of the insulating fine powder, it was confirmed by scanning a transmission electron microscope that SiO ₂ and ZrO ₂ films were formed. Further, in the same manner as in Synthesis Example 3 of the insulating fine powder, the volume resistivity of 3.1 mm was measured under a pressure of 38.2 MPa and the volume resistivity was 0.41 Ω. Cm.

(Synthesis Example 8 of Insulating Micropowder)

The mixed solution of the synthesis example 3 of the insulating fine powder was further synthesized in the same manner as in Synthesis Example 3 except that 150 g of a 1-propanol solution of tetrapropoxyzirconium was added to synthesize the insulating fine powder. In the same manner as in Synthesis Example 3 of the insulating fine powder, it was confirmed by scanning a transmission electron microscope that SiO ₂ and ZrO ₂ films were formed.

(Synthesis Example 9 of Insulating Micropowder)

In place of the insulating black powder, the carbon black of the synthesis example 3 was replaced with a carbon nanofiber (fiber having a cross-sectional diameter of 150 nm and a length of 5 to 6 μm), and the insulating carbonized carbon was synthesized in the same manner as in the synthesis example 3 of the insulating fine particles. Rice fiber (insulated fine powder). In the same manner as in Synthesis Example 3 of the insulating fine powder, it was confirmed by a scanning transmission electron microscope that the film of SiO ₂ was formed.

(Synthesis Example 10 of Insulating Micropowder)

The carbon black of the synthesis example 3 of the insulating fine powder was replaced with natural graphite (thickness of 100 to 200 nm, average thickness of 150 nm, angle of 1 to 3 μm, and plate shape of an average of 2 μm), and was carried out in the same manner as in Synthesis Example 3 of the insulating fine particles. Synthetic insulating natural graphite particles (insulated fine powder). In the same manner as in Synthesis Example 3 of the insulating fine powder, it was confirmed by a scanning transmission electron microscope that the film of SiO ₂ was formed. Further, in the same manner as in Synthesis Example 3 of the insulating fine powder, the volume resistivity of 3.0 mm thick was measured under a pressure of 38.2 MPa, and the volume resistivity was 0.09 Ω. Cm.

(Synthesis Example 11 of Insulating Micropowder)

In place of the insulating fine powder, 50 g of methanol and 130 g of ion-exchanged water were replaced with 140 g of methanol and 20 g of ion-exchanged water, and the insulating fine powder was synthesized in the same manner as in the synthesis example 3 of the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 12 of Insulating Micropowder)

50 g of methanol in the synthesis example 3 of the insulating fine powder was replaced with 50 g of isopropyl alcohol, and the insulating fine powder was synthesized in the same manner as in the synthesis example 3 of the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 13 of Insulating Micropowder)

In place of the 0.5 mol/l 5 g phosphoric acid reagent of Synthesis Example 3 of the insulating fine powder, a 0.5 g/l of 10 g acetic acid reagent was used instead, and the insulating fine powder was synthesized in the same manner as in Synthesis Example 3 of the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 14 of Insulating Micropowder)

In place of the 0.5 mol/l 5 g phosphoric acid reagent of Synthesis Example 3 of the insulating fine powder, 0.5 mol/l of 1 g hydrochloric acid reagent was used, and the insulating fine powder was synthesized in the same manner as in Synthesis Example 3 of the insulating fine powder. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 15 of Insulating Micropowder)

In the synthesis example 3 of the insulating fine powder, the insulating fine powder was synthesized in the same manner as in the synthesis example 3 of the insulating fine powder except that 40 g of tetraethoxysilane was not used. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 16 of Insulating Micropowder)

In the synthesis example 2 of the insulating fine powder, 70 g of tetraethoxy decane was used instead of 150 g of a tetrapropoxy zirconium 1-propanol solution, and the insulating fine powder was synthesized in the same manner as in the synthesis example 2 of the insulating fine powder. . In the same manner as in Synthesis Example 2 of the insulating fine powder, it was confirmed by scanning a transmission electron microscope that it was confirmed that a ZrO ₂ film was formed.

(Synthesis Example 17 of Insulating Micropowder)

In the synthesis example 2 of the insulating fine powder, 70 g of tetraethoxy decane was replaced by 110 g of titanium tetraisopropoxide (TPT, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the same procedure as in Synthesis Example 2 of the insulating fine powder was carried out. The synthetic insulating fine powder is synthesized. In the same manner as in Synthesis Example 2 of the insulating fine powder, it was confirmed by scanning a transmission electron microscope that the TiO ₂ film was formed.

(Synthesis Example 18 of Insulating Micropowder)

In the mixed solution of the synthesis example 2 of the insulating fine powder, 110 g of titanium tetraisopropoxide was used, and the insulating fine powder was synthesized in the same manner as in the synthesis example 2 of the insulating fine powder. In the same manner as in Synthesis Example 2 of the insulating fine powder, it was confirmed by scanning a transmission electron microscope that the film of SiO ₂ and TiO ₂ was formed.

(Synthesis Example 19 of Insulating Micropowder)

In the mixed solution of the synthesis example 3 of the insulating fine powder, 110 g of titanium tetraisopropoxide was used, and the insulating fine powder was synthesized in the same manner as in the synthesis example 3 of the insulating fine powder. In the same manner as in Synthesis Example 3 of the insulating fine powder, it was confirmed by scanning a transmission electron microscope that the film of SiO ₂ and TiO ₂ was formed.

(Synthesis Example 20 of Insulating Fine Powder)

In the mixed solution of the synthesis example 3 of the insulating fine powder, the insulating fine powder was synthesized in the same manner as in the synthesis example 3 of the insulating fine powder except that 0.5 g/l of 5 g of phosphoric acid was not used. The SiO ₂ film was confirmed to have been observed by a scanning transmission electron microscope in the same manner as in Synthesis Example 3 of the insulating fine powder.

(Synthesis Example 21 of Insulating Fine Powder) The method of synthesizing the method for synthesizing the ultrafine powder of JP-A-2011-49141

Using a 5 L glass reaction vessel, 100 g of carbon black (spherical particle diameter: 5 to 100 nm, average particle diameter: 40 nm) and 100 g of titanium tetraisopropoxide in 800 g of methanol were added, and the mixture was stirred and mixed at 30 ° C for 1 hour. Then, 10 g of an alkoxy metal (KBM-103 (phenyltrimethoxydecane), manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed for 30 minutes. Further, 30 g of distilled water was dropped over 30 minutes, and the mixture was stirred for 2 hours to obtain a carbon black particle/methanol dispersion.

Then, a vacuum filtration flask was used for solid-liquid separation, and the wet cake was dried in a vacuum dryer. The obtained carbon black particles were observed by a scanning transmission electron microscope in the same manner as in the synthesis method 2, and it was confirmed that a film which is considered to be derived from TiO ₂ was formed on the surface of the carbon black.

When the filtrate after the solid-liquid separation was distilled off with a solvent, a solid content in the form of a sand glass was obtained. The solid content of the obtained glassy glass was further dried, and elemental analysis was carried out by a scanning electron microscope (JSM-6460 LA, manufactured by JEOL Ltd.) using an energy dispersive X-ray analyzer, and the peak value as a main element was detected. Si. Further, in the same manner as in Synthesis Example 3 of the insulating fine powder, the volume resistivity of 3.2 mm thick was measured at a pressure of 38.2 MPa and the volume resistivity was 0.48 Ω. Cm.

(Synthesis Example 22 of Insulating Fine Powder)

2 kg of carbon black (spherical particle diameter: 50 to 100 nm, average particle diameter: 70 nm, SEASTS manufactured by Tokai Carbon Co., Ltd.) and 2.1 kg of tetraethoxysilane were placed in 40 L of isopropanol, and the mixture was stirred and stirred at room temperature for 1 hour. The dispersion solution was dropped over 2 hours with 2 kg of distilled water, and further stirred for 2 hours. Although the aqueous isopropanol was distilled under a vacuum of 17 kPa, 45 L of N,N-dimethylacetamide was added dropwise to replace the solvent. Further, 0.31 kg of phenyltrimethoxydecane was added, and the mixture was heated and hydrophobized at 100 ° C for 4 hours, then naturally dried by filtration for 12 hours, and calcined at 350 ° C for 30 minutes in a nitrogen atmosphere. As a result, a surface treatment of 2.8 kg was carried out to obtain an insulating fine powder. The insulating fine powder was observed by a scanning transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.), and it was confirmed that a SiO ₂ film was formed on the surface of the carbon black.

In the synthesis examples 1 to 22 of the above insulating fine powder, the raw materials used and the production conditions are collectively shown in Table 1.

Alkoxy metal A: alkoxy metal having four alkoxy groups in one molecule

Alkoxy metal B: alkoxy metal having three alkoxy groups in one molecule

CB: carbon black

CNF: carbon nanofiber

CBG: natural graphite

CBS: carbon black, SEATS

KBE-04: tetraethoxy decane

ZA-45: tetrapropoxy zirconium 75 mass% solution

TPT: titanium tetraisopropoxide

KR-510: an oligomer composed of methyltrimethoxydecane and phenyltrimethoxydecane

KC-89S: oligomer of methyltrimethoxydecane

X-41-1056: an oligomer composed of methyltrimethoxydecane and γ-glycidoxypropyltrimethoxydecane

KBM-103: Phenyltrimethoxydecane

MeOH: methanol

IPA: isopropanol

DMC: N,N-dimethylacetamide

(Example 1)

The insulating fine powder obtained in Synthesis Example 1 was melt-kneaded together with a polycarbonate resin (IUPILONS-3000 FN, manufactured by Mitsubishi Engineering Plastics Co., Ltd., referred to as PC) at 300 ° C in a melt kneading machine. It became a volume ratio of the insulating fine powder/PC = 25/75, and a pelletized resin composite material was obtained.

The obtained pellet was measured for MVR (mass volume rate) at a temperature of 300 ° C and a load of 1.2 kg of 9 cm ³ / 10 minutes.

Further, the obtained pellets were molded into a disk-shaped molded piece on an injection molding machine, and the dielectric ratio of the molded sheet was measured at a dielectric constant of 12 and a dielectric loss of 0.028 at 1 MHz. Further, the specific gravity of the resin composite material was 1.35.

(Example 2)

The insulating fine powder obtained in Synthesis Example 2 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together at 300 ° C in a melt kneader to be an insulating fine powder/PC. Volume ratio = 25/75 A pelletized resin composite material is obtained.

The obtained pellet was measured for MVR (mass volume rate) at a temperature of 300 ° C and a load of 1.2 kg of 9 cm ³ / 10 minutes.

Further, the obtained pellets were molded into a disk-shaped molded piece on an injection molding machine, and the dielectric ratio of the molded pellet was measured at a dielectric constant of 12 and a dielectric loss of 0.015 at 1 MHz. Further, the specific gravity of the resin composite material was 1.35.

(Example 3)

The insulating fine powder obtained in Synthesis Example 2 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together at 300 ° C in a melt kneader to be an insulating fine powder/PC. The volume ratio = 20/80 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 12 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 7, and the dielectric loss was 0.012. Further, the specific gravity of the resin composite material was 1.32.

(Example 4)

The insulating fine powder obtained in Synthesis Example 2 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together at 300 ° C in a melt kneader to be an insulating fine powder/PC. The volume ratio = 30/70 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 6 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 17, and the dielectric loss was 0.018. Further, the specific gravity of the resin composite material was 1.38.

(Example 5)

The insulating fine powder obtained in Synthesis Example 3 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to be an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

25 g of the pulverized product obtained by pulverizing the molded piece of the resin composite material was added to 500 ml of a methanol solution of 10% by mass of potassium hydroxide, and refluxed for 24 hours to carry out hydrolysis treatment. The hydrolyzed solution was filtered, and the mixed insulating fine powder was collected, washed with pure water until the washing liquid became neutral, and dried at 120 ° C for 24 hours. The obtained insulating fine powder was measured in the same manner as in Synthesis Example 3 of the insulating fine powder, and the volume resistivity of the 2.8 mm thick was measured to be 0.09 Ω under a pressure of 38.2 MPa. Cm. The state of the raw material before melt-kneading is almost the same volume resistance value, confirming the insulation film It is not easy to be damaged.

(Example 6)

The insulating fine powder obtained in Synthesis Example 4 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneading machine to be an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 13 and the dielectric loss was 0.016. Further, the specific gravity of the resin composite material was 1.35.

(Example 7)

The insulating fine powder obtained in Synthesis Example 5 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to obtain an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Example 8)

The insulating fine powder obtained in Synthesis Example 6 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together at 300 ° C in a melt kneader to be an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 9 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Example 9)

The insulating fine powder obtained in Synthesis Example 7 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together at 300 ° C in a melt kneader to be an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 14 and the dielectric loss was 0.012. Further, the specific gravity of the resin composite material was 1.36.

(Embodiment 10)

The insulating fine powder obtained in Synthesis Example 8 was used in Example 1 The polycarbonate resin (PC) was melt-kneaded together at 300 ° C in a melt kneading machine to have a volume ratio of insulating fine powder/PC = 25/75 to obtain a pelletized resin composite material.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 13 and the dielectric loss was 0.013. Further, the specific gravity of the resin composite material was 1.37.

(Example 11)

The insulating fine powder obtained in Synthesis Example 9 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together at 300 ° C in a melt kneading machine to become an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 11 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Embodiment 12)

The insulating fine powder obtained in Synthesis Example 10 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to obtain an insulating fine powder/PC. Volume ratio = 25/ 75. A granulated resin composite material is obtained.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Example 13)

The insulating fine powder obtained in Synthesis Example 11 and the polycarbonate resin (PC) used in Example 1 were melt-kneaded together in a melt kneader at 300 ° C to become an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 9 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Example 14)

The insulating fine powder obtained in Synthesis Example 12 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to be an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Example 15)

The insulating fine powder obtained in Synthesis Example 13 was melt-kneaded at 350 ° C in a melt kneading machine together with the polycarbonate resin (PC) used in Example 1 to obtain an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 9 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 12 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Embodiment 16)

The insulating fine powder obtained in Synthesis Example 14 was melt-kneaded at 350 ° C in a melt kneading machine together with the polycarbonate resin (PC) used in Example 1 to become an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 9 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric constant was measured at 1 MHz. For a specific dielectric ratio of 12, the dielectric loss is 0.015. Further, the specific gravity of the resin composite material was 1.35.

(Comparative Example 1)

The insulating fine powder obtained in Synthesis Example 15 was melt-kneaded at 350 ° C in a melt kneading machine together with the polycarbonate resin (PC) used in Example 1 to become an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio of the dielectric ratio was >100 and the dielectric loss was >0.2 at 1 MHz. Further, the specific gravity of the resin composite material was 1.35.

(Comparative Example 2)

The insulating fine powder obtained in Synthesis Example 16 was melt-kneaded at 350 ° C in a melt kneading machine together with the polycarbonate resin (PC) used in Example 1 to become an insulating fine powder/PC. When the volume ratio is 25/75, when the granulation is carried out, the resin is decomposed, so that granulation cannot be performed, and injection molding cannot be performed, and MVR cannot be measured.

(Comparative Example 3)

The insulating fine powder obtained in Synthesis Example 17 was mixed with the polycarbonate resin (PC) used in Example 1 in a melt kneader at 300 ° C. The melt-kneading was carried out so that the volume ratio of the insulating fine powder/PC was 25/75. When the granulation was carried out, the resin was decomposed, so that it was impossible to pelletize, and injection molding could not be performed, and MVR could not be measured.

(Comparative Example 4)

The insulating fine powder obtained in Synthesis Example 18 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to obtain an insulating fine powder/PC. When the volume ratio is 25/75, when the granulation is carried out, the resin is decomposed, so that it cannot be granulated, and injection molding cannot be carried out, and the MVR cannot be measured.

(Comparative Example 5)

The insulating fine powder obtained in Synthesis Example 19 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to be an insulating fine powder/PC. When the volume ratio is 25/75, when the granulation is carried out, the resin is decomposed, so that it cannot be granulated, and injection molding cannot be carried out, and the MVR cannot be measured.

(Comparative Example 6)

The insulating fine powder obtained in Synthesis Example 20 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneader to obtain an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR was measured in the same manner as in Example 1 and the MVR was 10 cm ³ /10 minutes.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio of the dielectric ratio was >100 and the dielectric loss was >0.2 at 1 MHz. Further, the specific gravity of the resin composite material was 1.35.

(Comparative Example 7)

The insulating fine powder obtained in Synthesis Example 21 of the insulating fine powder and the polycarbonate resin (PC) used in Example 1 were melt-kneaded at 300 ° C in a melt kneading machine to be insulated. When the volume ratio of the fine powder/PC is 25/75, when the granulation is carried out, the resin is decomposed, so that it cannot be granulated, and injection molding cannot be carried out, and the MVR cannot be measured.

(Comparative Example 8)

The insulating fine powder obtained in Synthesis Example 22 was melt-kneaded together with the polycarbonate resin (PC) used in Example 1 at 300 ° C in a melt kneading machine to become an insulating fine powder/PC. The volume ratio = 25/75 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 1 to be 10 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 13 and the dielectric loss was >0.2. Further, the specific gravity of the resin composite material was 1.34.

(Example 17)

The insulating fine powder obtained in Synthesis Example 3 was melt-kneaded together with polyethylene terephthalate resin (manufactured by Mitsubishi Chemical Corporation, NovaPEX GG900, PET) at 270 ° C in a melt kneader. It became a volume ratio of insulating fine powder/PET = 25/75, and a pelletized resin composite material was obtained.

The obtained pellet was measured for MVR (mass volume rate) at 270 ° C and a load of 1.2 kg to be 12 cm ³ / 10 minutes.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 15 and the dielectric loss was 0.016. Further, the specific gravity of the resin composite material was 1.47.

(Embodiment 18)

The insulating fine powder obtained in Synthesis Example 3 and the polyethylene terephthalate resin (PET) used in Example 17 were melt-kneaded at 270 ° C in a melt kneading machine to be insulated. The volume ratio of the fine powder/PET = 30/70, and a pelletized resin composite material was obtained.

The MVR was measured in the same manner as in Example 16 to be 9 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 20, and the dielectric loss was 0.019. Further, the specific gravity of the resin composite material was 1.51.

(Embodiment 19)

The insulating fine powder obtained in Synthesis Example 4 was melt-kneaded together with polybutylene terephthalate resin (Mitsubishi Engineering Plastics Co., Ltd., NovaDuran 5008, PBT) at 270 ° C in a melt kneader. The volume ratio of the insulating fine powder/PBT was changed to 25/75 to obtain a pelletized resin composite material.

The obtained pellet was measured for MVR (mass volume rate) at 270 ° C and a load of 1.2 kg, and the result was 12 cm ³ / 10 minutes.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 16 and the dielectric loss was 0.016. Further, the specific gravity of the resin composite material was 1.47.

(Embodiment 20)

The insulating fine powder obtained in Synthesis Example 4 and the polybutylene terephthalate resin (PBT) used in Example 19 were melt-kneaded at 270 ° C in a melt kneading machine to be insulated. The volume ratio of the fine powder/PBT = 30/70, and a pelletized resin composite material was obtained.

The MVR result was measured in the same manner as in Example 18 to be 9 cm ³ /10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 19, and the dielectric loss was 0.019. Further, the specific gravity of the resin composite material was 1.52.

(Example 21)

Insulating fine powder obtained in Synthesis Example 5 and polyphenylene ether resin (manufactured by Mitsubishi Chemical Corporation, UPS PX100L, PPE), and polystyrene resin (PSJ-polystyrene GPPS HF77, manufactured by PS Japan Co., Ltd.) , PS) was melt-kneaded together at 270 ° C in a melt kneader to have a volume ratio of insulating fine powder / PPE / PS = 25 / 37.5 / 37.5 to obtain a pelletized resin composite.

The obtained pellets were measured for MVR (mass volume rate) at 270 ° C and a load of 1.2 kg, and the result was 14 cm ³ / 10 minutes.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 15 and the dielectric loss was 0.012. Further, the specific gravity of the resin composite material was 1.24.

(Example 22)

The insulating fine powder obtained in Synthesis Example 5 was melt-kneaded together with the polyphenylene ether resin (PPE) used in Example 21 and polystyrene resin (PS) in a melt kneader at 270 ° C. The volume ratio of the insulating fine powder/PPE/PS was changed to 30/35/35 to obtain a pelletized resin composite material.

The MVR result was measured to be 12 cm ³ / 10 minutes in the same manner as in Example 20.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to have a dielectric constant of 18 and a dielectric loss of 0.015. Further, the specific gravity of the resin composite material was 1.28.

(Example 23)

The insulating fine powder obtained in Synthesis Example 2 was melt-kneaded together with a polyphenylene sulfide resin (manufactured by Toray Industries, Inc., Toray Lina M2888, PPS) at 290 ° C in a melt kneading machine. The volume ratio of the insulating fine powder/PPS was changed to 25/75 to obtain a pelletized resin composite material.

The obtained pellets were measured for MVR (mass volume rate) at 290 ° C and a load of 1.2 kg, and the result was 15 cm ³ / 10 minutes.

A molded piece was obtained in the same manner as in Example 1, and the dielectric constant was measured at 1 MHz to have a dielectric constant of 15 and a dielectric loss of 0.009. Further, the specific gravity of the resin composite material was 1.46.

(Example 24)

The insulating fine powder obtained in Synthesis Example 2 was melt-kneaded at 290 ° C in a melt kneading machine together with the polyphenylene sulfide resin (PPS) used in Example 23 to become an insulating fine powder/PPS. The volume ratio = 30/70 gave a pelletized resin composite.

The MVR result was measured in the same manner as in Example 22 to be 12 cm ³ / 10 min.

A molded piece was obtained in the same manner as in Example 1, and the dielectric ratio was measured at 1 MHz to be a dielectric constant of 25 and a dielectric loss of 0.013. Further, the specific gravity of the resin composite material was 1.49.

(Embodiment 25)

The insulating fine powder obtained in Synthesis Example 2 was melt-kneaded at 220 ° C in a melt kneading machine together with a polypropylene resin (Prime Polypro J106G, PP, manufactured by Prime Polymer Co., Ltd.) to become an insulating fine powder. The volume ratio of /PP was changed to 25/75 to obtain a pelletized resin composite material.

The obtained pellets were measured for MVR (mass volume rate) at 220 ° C and a load of 1.2 kg, and the result was 15 cm ³ / 10 minutes.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 10, and the dielectric loss was 0.009. Further, the specific gravity of the resin composite material was 1.08.

(Example 26)

The insulating fine powder obtained in Synthesis Example 2 was melt-kneaded at 220 ° C in a melt kneading machine together with the polypropylene resin (PP) used in Example 25 to obtain a volume ratio of the insulating fine powder/PP. = 30/70, a pelletized resin composite is obtained.

The MVR result was measured in the same manner as in Example 24 to be 12 cm ³ / 10 min.

A molded piece was obtained in the same manner as in Example 1. The dielectric ratio was measured at 1 MHz and the dielectric loss was 14 and the dielectric loss was 0.013. Further, the specific gravity of the resin composite material was 1.12.

The results of the above Examples 1 to 26 and Comparative Examples 1 to 8 are summarized in Table 2.

PC: polycarbonate resin

PET: polyethylene terephthalate resin

PBT: polybutylene terephthalate resin

PPE: Polyphenylene ether resin

PS: Polystyrene resin

PPS: Polyphenylene sulfide resin

PP: polypropylene resin

[Industry use possibility]

According to the present invention, it is possible to provide a dielectric constant of a resin composite material which can maintain a high state at the same time and to reduce a dielectric loss tan δ , and to promote a sol-gel reaction due to a specific reaction condition, and heat-melt-mix with a resin. A high dielectric ratio resin composite material which does not cause resin decomposition of the insulating fine powder, and a method for producing the same. Moreover, since the resin composite material of the present invention uses a carbon material on the raw material of the insulating fine powder, the specific gravity can be reduced to 2 or less.

Therefore, the resin composite material of the present invention can be used for the production of molded articles having high dielectric constants or various molded articles such as radio wave absorbers, antenna substrates, non-contact IC cards/tags, and the like in the electrical field or the electronic field.

Fig. 1 is a scanning electron micrograph of the insulating fine powder obtained in Synthesis Example 3 of the insulating fine powder. In the portion from 1 to 3 in the photograph, the ratio of Si measurement to C measurement is expressed as Si/C ratio according to energy dispersive X-ray spectrometry.

Fig. 2 is a scanning electron micrograph of carbon black (spherical particle diameter: 5 to 100 nm, average particle diameter: 40 nm) of the raw material of Synthesis Example 3 for insulating fine powder. In the portion of the photograph 1, the ratio of Si metering to C metering is expressed as Si/C ratio according to energy dispersive X-ray spectrometry.

Claims (22)

A resin composite material comprising a resin composition containing the following insulating fine powder and a resin, wherein the insulating fine powder contains a conductive fine powder, an acid, an alkoxy group formed of a carbon material. The metal composition and the mixture of water are obtained by distilling off a solvent containing water, wherein the content of the tetraalkoxy decane in the metal alkoxide composition is 15% by mass or more, and the content of the titanium alkoxide The amount is 10% by mass or less, and the volume ratio of the insulating fine powder to the resin is 5/95 to 50/50 (insulating fine powder/resin). The resin composite material of claim 1, wherein the mixture contains an alcohol. The resin composite material according to claim 1 or 2, wherein the mixture further contains tetraalkoxy zirconium. The resin composite material according to any one of claims 1 to 3, wherein the mixture further contains a trialkoxydecane. The resin composite material according to claim 4, wherein the trialkoxysilane has a molecule selected from the group consisting of a methyl group, a phenyl group, a vinyl group, an isobutyl group, a decyl group, a glycidoxy group, an amine group, One or more types of decane coupling agents in which a thiol group and a methacryloxy group are grouped. The resin composite material according to any one of claims 1 to 5, wherein the alkoxide metal composition is free of alkoxytitanium. The resin composite material according to any one of claims 1 to 6, wherein the conductive fine powder is nano carbon fiber, natural black lead, carbon black, carbon nanotube or artificial black lead. The resin composite material according to any one of claims 2 to 7, wherein the mixture contains an acidic aqueous solution containing an alcohol, a conductive fine powder composed of a carbon material, and an alkoxy metal composition. The alcohol-containing acidic aqueous solution contains an alcohol, an acid, and water, wherein the acidic aqueous solution containing the alcohol is at pH 3 or higher and does not reach pH 7. The resin composite material according to any one of claims 1 to 8, wherein the aforementioned resin is a thermoplastic resin. The resin composite material according to claim 9, wherein the thermoplastic resin is polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyphenylene sulfide, Or polypropylene. The resin composite material according to any one of claims 1 to 10, wherein the resin composition contains a filler. The resin composite material according to any one of the items 1 to 11, wherein the insulating fine powder has a cross-sectional diameter of 1 nm or more and 500 nm or less. The resin composite material according to any one of claims 1 to 12, wherein the specific gravity is 2 or less. The resin composite material according to any one of claims 1 to 13, wherein the specific dielectric constant is 7 or more. The resin composite material according to any one of claims 1 to 14, wherein the dielectric loss tan δ is less than 0.1. A method for producing an insulating fine powder characterized by mixing a conductive fine powder made of a carbon material, an acid, an alkoxy metal composition, The mixture of the water and the mixture is stirred, and after the solvent is distilled off, the content of the tetraalkoxy decane in the metal alkoxide composition is 15% by mass or more, and the content of the titanium alkoxide is 10% by mass or less. The method for producing an insulating fine powder according to claim 16, wherein the mixture contains an alcohol. The method for producing an insulating fine powder according to claim 16 or 17, wherein the mixture further contains tetraalkoxy zirconium. The method for producing an insulating fine powder according to any one of claims 16 to 18, wherein the mixture further contains a trialkoxydecane. The method for producing an insulating fine powder according to any one of claims 16 to 19, wherein the alkoxide metal composition does not contain titanium alkoxide. The method for producing an insulating fine powder according to any one of claims 17 to 20, which is an alcohol-containing acidic aqueous solution containing an alcohol, an acid, and water in an amount of not more than pH 7 and having a pH of 3 or higher. A method for producing a resin composite material, characterized in that the insulating fine powder obtained by the production method according to any one of claims 16 to 21 is added to the resin to a volume ratio of the resin of 5/ 95~50/50 (insulated fine powder/resin).