JP2802424B2 - Dielectric or piezoelectric composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric or piezoelectric composition comprising a metal titanate fiber and a binder and a molded product thereof, and more particularly to a composition comprising a metal titanate fiber and a curable binder. Dielectric or piezoelectric curable composition, dielectric or piezoelectric coating composition comprising a metal titanate fiber and a binder capable of forming a coating, and dielectric comprising a metal titanate fiber and a binder Alternatively, the present invention relates to a composite sheet having piezoelectricity.

[0002]

In recent years, there have been remarkable developments in dielectric materials and piezoelectric materials accompanying the development of the electronics industry. Various materials having dielectric properties and piezoelectric properties are known. The ceramic-based, quartz, Rochelle salt _{(NaKC 4 HO 6 · 4H 2} O), BaTiO 3 system, PZ
T-type (PbTiO ₃ -PbZrO ₃ ), CdS, ZnO and the like are known. Industrially, BaTiO ₃ or PZT
Dielectric porcelain and piezoelectric porcelain obtained by sintering system materials are used in large quantities. However, polymer dielectrics, polymer piezoelectrics, and the like have been developed because they are not energy saving due to sintering at a high temperature and do not have free shaping properties. Polymer dielectrics and polymer piezoelectrics have the following features. In other words, it must be flexible. It can produce products of various shapes. It has good mechanical consistency with the human body and water. It can have a large area. It can make thin films. It has features that ceramics do not have, such as being able to give.

[0003] There are two main types of polymer dielectrics and polymer piezoelectrics, one of which is a group in which the polymer itself has dielectric and piezoelectric properties. Specific examples thereof include polyvinylidene fluoride, cyanoethylated polyol, polyvinylphosphabenzene,
Examples include polyvinyl quinoline, vinylidene cyanide / vinyl acetate copolymer, vinylidene fluoride / trifluoroethylene copolymer, and the like. However, these polymer dielectric / piezoelectric materials have a problem that the relative permittivity is 13 or 1200, which is lower than that of a typical example of polyvinylidene fluoride, which is a ceramic-based PZT-based material.

[0004] Therefore, the development of materials that combine the characteristics of polymer dielectric / piezoelectric materials with the characteristics of ceramic dielectric / piezoelectric materials has been actively pursued. As another polymer dielectric / piezoelectric material, there can be mentioned the above-mentioned composite dielectric / piezoelectric material. Composite dielectric / piezoelectric materials make use of both the workability and flexibility of ceramic ferroelectric / piezoelectric powders and polymers. Conventionally known ceramic-based materials include BaTiO ₃ -based, PZT-based, and the like. Typical conventionally known polymers include polyvinylidene fluoride-related polymers having a high dielectric constant, rubber, and thermoplastic resins.

In general, the dielectric constant, piezoelectric constant, and the like of a composite in which fine ceramic powder is dispersed in a polymer matrix increase in proportion to the amount of ceramic mixed. Therefore, when trying to obtain a high dielectric constant or a piezoelectric constant, the ratio of polymer / ceramic becomes extremely small, and the disadvantage of losing the characteristics of a composite dielectric / piezoelectric material as a polymer composition occurs. Remained unresolved.

Also, Japanese Patent Application Laid-Open No. 56-162403 proposes barium titanate particles elongated in the crystal axis direction, which can exhibit a remarkable anisotropy of dielectric properties in the crystal axis direction. Expected. However, the above publication does not actually attempt to form a composite with a resin, and does not know what effect is actually obtained. In addition, the technical idea disclosed in the above-mentioned publication is that the fibers are elongated in the crystal axis direction, so that the dielectric properties in a specific direction can be improved. Therefore, in order to enjoy such effects, the fibers need to be oriented in a specific direction, and even if the effects predicted by the publication are actually obtained, they can be used only for extremely limited applications. It is.

[0007]

According to the present invention, there is provided a compound represented by a general formula MO
n (Ti, X) O ₂ (where M is a metal element of one or more divalent ions, X is zero or zirconium, n
Is a real number) having a fiber length of 1 to 1000 μm and a fiber diameter of 0.01 to 10 μm (excluding the case of lead zirconate titanate whiskers) and a dielectric or According to the present invention, it has been clarified that, according to the present invention, a dielectric or piezoelectric resin composition having excellent workability and mechanical strength can be obtained.

According to the present invention, a general formula MO · n (Ti, X) O ₂ (wherein
M is a metal element of a single or a plurality of divalent ions, X is zero or zirconium, and n is an integer.

The metal titanate fiber of the present invention is obtained by forming a metal titanate, which is a conventionally known fine powder of ferroelectric ceramics, into a fibrous shape such as a whisker shape. The diameter is also different depending on the purpose of use and is not specified, but the fiber length is usually 1 to 1000 μm, preferably 2 to 50 μm, and the fiber diameter is usually 0.01 to 10 μm.
m, preferably 0.1 to 2 μm, and a fiber length / fiber diameter ratio of about 20 to 100 is preferable.

In particular, long-fiber whiskers are more excellent as a reinforcing effect, but are generally fine and have a high aspect ratio (fiber length / fiber diameter) because the porosity at the time of close packing is large and it is difficult to obtain a homogeneous resin composition. Is preferred, but most of the currently available ones have a fiber diameter of 0.1 to 2 μm and a fiber length of about 1 to 20 μm, and these can be sufficiently applied in the present invention.

By employing such a metal titanate fiber as a ferroelectric, the desired dielectric and piezoelectric characteristics can be obtained even if the amount of addition is smaller than that of a conventional ferroelectric fine powder. The dielectric or piezoelectric resin composition of the present invention has good processability and high mechanical properties of the obtained molded product, which is a completely new feature that can be achieved for the first time by the present invention.

That is, the inventors of the present invention have conducted intensive studies on the compounding of a dielectric material and a resin by blending a high dielectric substance with a resin. As a result, regardless of the direction of crystal axis elongation and the direction of fiber orientation, It has been found that the incorporation of a fibrous dielectric can significantly improve the dielectric constant as compared with the case of incorporating a powdery dielectric. That is, according to the present invention, it is possible to obtain a resin composition having a higher dielectric constant than the conventional one by a molding method in which the orientation direction of the fiber is not constant, such as injection molding, blow molding, and press molding.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the metal titanate fiber represented by the above general formula in the present invention, specific examples of the metal element represented by M include Ba, Ca, Sr, Mg, Zn, C
One or a combination of two or more selected from the group consisting of o, Ni, Be, Cd and Pb can be mentioned.
Therefore, typical compounds of the metal titanate fiber of the present invention can be exemplified by ferroelectric metal titanate-based fibers such as magnesium titanate, barium titanate, strontium titanate, and lead titanate. Can be exemplified by lead zirconate titanate.

In the present invention, the above-mentioned various ferroelectric or piezoelectric fibers obtained by adding another divalent metal element as a dopant can also be used. Furthermore, these ferroelectric fibers or piezoelectric fibers alone,
Alternatively, they can be used in combination.

A typical example of the method for synthesizing the metal titanate fiber represented by the above general formula employed in the present invention will be described.

1) Synthesis example of barium titanate fiber This is a synthesis method disclosed in JP-A-55-113623, wherein water is added to powdered titanium dioxide and anhydrous potassium carbonate.
The well-kneaded product is dried and fired at 1000 ° C. for 24 hours. After cooling, it is put into water, and the fibrous material is defibrated by stirring. This is filtered and dried to obtain potassium titanate hydrate whisker.

Next, the thus obtained potassium titanate hydrate whisker, barium hydroxide and water were charged into an autoclave and kept at 500 ° C. for 20 hours. After the reaction, the rapidly cooled sample was taken out, filtered, washed with water, and dried at 80 ° C. overnight to obtain barium titanate fiber. The ratio between the fiber length and the fiber diameter of the obtained barium titanate fiber was at least 10 or more.

2) Synthesis example of lead zirconate titanate whisker Since lead zirconate titanate is a cubic crystal, PbO and Ti
It has been found that only equiaxed particles can be synthesized by the reaction of O ₂ and ZrO ₂ , but needle-like particles can be obtained by synthesizing TiZrO _{4 in} a flux. The needle-shaped TiZrO ₄ and PbO were dry-mixed and fired at 800 to 900 ° C. for about 1 hour to obtain lead zirconate titanate whiskers. S
Observation with an EM photograph showed that the ratio between the fiber length and the fiber diameter was at least 10 or more.

In the first embodiment of the present invention, the general formula MO.
By bonding a metal titanate fiber represented by n (Ti, X) O ₂ (wherein M, X and n are the same as above) with a curable binder, a cured material having desired dielectric and piezoelectric properties can be obtained. To obtain a conductive resin composition. Such a curable binder binds the metal titanate fiber and other components to be added as required to provide moldability and / or determines the support, and includes the presence of a catalyst, Or, in the absence, it becomes a high molecular weight with a chemical reaction or crosslinks to become an insoluble, infusible binder, and is generally activated by various external energies such as heat, light, and electron beam. However, some are activated under a special atmosphere such as the presence of moisture in the atmosphere and the presence or absence of oxygen even at room temperature or lower.

As the curable binder of the present invention, an organic curable resin is usually suitable, but an inorganic curable binder may be used as long as it has workability and bonding strength.

Accordingly, the binder of the present invention generally comprises heat,
It has a cross-linking point that causes a chemical reaction by light, an electron beam, and / or a catalyst to become a macromolecule, and a reactive group having a reactive activity exists as the cross-linking point. Representative examples of these reactive groups include a hydroxyl group, an alkoxy group, a carboxyl group, an amino group, a nitrile group, an unsaturated group such as an epoxy group and a vinyl group, an acetyl group and derivatives thereof, and substituted organic compounds in an organometallic compound. And usually one or more of these reactive groups coexist.

Accordingly, the curable binder of the present invention is not particularly limited as long as it can be cured by reaction at a reactive active site.
Typical examples are 1) amino resin, 2) phenolic resin, 3) alkyd resin, 4) epoxy resin, 5) urethane resin, 6) polyamide resin, 7) polyester resin, 8) vinyl resin, 9) Polyimide resin, 10) polymercapto resin,
11) silicone resin, 12) fluorine resin, 13) boron resin, 1
4) Organo-titanium resin, 15) One or more mixtures of inorganic curable substances such as silicates, phosphates, borates and the like, and precursors thereof, which are heat, light, electron beam, catalyst And the like, which hardens to form an insoluble and infusible binder.

The curable binder of the present invention is often provided as a precursor before insolubilizing or infusing, due to the convenience of processability, and is usually a solid powder, a liquid, a solution containing a solvent, or a dispersion. Dispersions or emulsions, including media, more particularly, are provided or used as gases. Some of these materials are unstable at room temperature and in a natural atmosphere and react immediately to cure, or to cure by mixing two or more kinds, to cure by adding a catalyst, etc. Some of them react without giving external energy, and for those with such remarkable reactivity, the environment that suppresses the reaction, for example, inert gas atmosphere, cold and dark place storage, addition of reaction inhibitor, catalyst and two or more It is necessary to separate and store the reaction components consisting of
Any material may be used as long as the metal titanate fiber of the present invention is bonded and cured.

Further, in the present invention, a colorant, a dispersant, a catalyst,
Co-catalysts, plasticizers, antioxidants, anti-aging agents, reaction inhibitors, reinforcing fillers, non-reinforcing fillers, and other commonly used additives may be used in combination. A reinforcing and / or non-reinforcing ferroelectric material may be used in addition to the metal salt fiber.

According to the present invention, a curable composition having dielectric or piezoelectric properties is obtained by bonding metal titanate fiber with a curable binder. The mixing ratio cannot be specified depending on the purpose of use and the type of the metal titanate fiber and the curable binder. If the amount of the binding agent is too small, the bonding strength is insufficient, and the strength of the molded body or the like is insufficient. Therefore, the range of 10 to 2000 parts, preferably 50 to 1000 parts, of the metal titanate fiber is practical with respect to 100 parts by weight of the binder (hereinafter, part by weight is abbreviated as part). However, since the metal titanate fiber of the present invention exhibits various colors and is an excellent reinforcing filler, it is possible to make use of these reinforcing properties and / or hues and to harden without substantially using electrical properties. Even if the composition relies on another dielectric material for its dielectric or piezoelectric properties, it is included in the resin composition of the present invention.

Even if a thermoplastic resin compatible with or phase-separable with the curable binder is used in addition to the curable binder, if the curable binder forms an essential component of the composition, These thermoplastic resins may be used in combination.

The method for producing the dielectric or piezoelectric resin composition of the present invention depends on the purpose of use and the type of curable binder, and cannot be specified.
Under a stable and easy-to-operate condition and atmosphere, a mixing machine that normally uses a metal titanate fiber and a curable binder,
It is obtained by mixing or dispersing with a dispersing machine and then treating it under curing conditions, and a catalyst, a solvent, a dispersing medium and other various additives which are usually used at the time of such mixing and dispersing can be added as necessary.

The curable binder or its precursor is generally unstable, and when two or more curable binders are used in combination or partially or entirely, when the metal titanate fiber or When mixing other additives, catalysts, and the like, some of them are cured at room temperature and in a natural atmosphere. In such a case, they should be separated and stored until immediately before use, and mixed immediately before use.

The curable composition of the present invention is prepared by heating the curable binder if the curable binder is thermosetting, or the ultraviolet ray if the curable binder is photocurable.
The desired dielectric or piezoelectric curable composition can be obtained by treatment with electron beams or in a special atmosphere, such as moisture curability or anaerobic curability, if desired. It may be performed under pressure or under pressure. In addition, the curable composition having dielectric or piezoelectric properties of the present invention can be used not only as one kind or two or more kinds of composites, but also as a composite fixed to the surface of the support layer, and is generally used for coating. , Coating, printing, and other commonly used molding methods can be applied. It is also important that the resin composition having dielectric or piezoelectric properties of the present invention is formed into an electret by applying an electric field or the like to the molded product.

The resin composition having dielectric or piezoelectric properties of the present invention has heat resistance, chemical resistance, surface smoothness of a molded product,
It has excellent strength and durability, and can replace ceramics as a dielectric or piezoelectric material, as well as improve the performance of conventionally known polymer dielectric and piezoelectric materials.
It has extremely high industrial applicability.

The second embodiment of the present invention relates to a metal titanate fiber and a binder capable of forming a coating (hereinafter referred to as "substrate").
And a coating composition having dielectric or piezoelectric properties.

These substrates according to the present invention are different depending on the purpose of use of the coating composition, but there are a soft substrate forming a soft coating layer and a hard substrate forming a hardening coating layer. The soft substrate of the present invention includes 1) amorphous or low-melting-point hydrocarbon compounds such as petrolatum, lanolin, petrolatum, and bituminous compounds or derivatives thereof, 2) fatty acids such as fatty acids and glycerin esters of fatty acids, and 3 4) Polyalkylene oxides comprising homopolymers or copolymers of alkylene oxides such as ethylene oxide and propylene oxide; 4) Fatty acids and alkylpolyalkylene oxides to which fatty acid glycerine oxide and alkylene oxide are added; or derivatives thereof; 5) Liquid polyethylene, liquid polypropylene , Liquid acrylic resin, tributyl phosphate, etc.
Compounds that are liquid or plastic at room temperature are exemplified, and these are used as one kind or as a mixture of two or more kinds.

The hard substrate of the present invention has a film-forming ability under the conditions of use atmosphere, and is generally used for paints, inks,
A binder used for an adhesive, a sealant, a molding material, or the like can be used as it is. Examples of the hard substrate of the present invention include higher fatty acids and derivatives thereof, polyolefin resins, alkyd resins, acrylic resins, vinyl resins, vinylidene resins, polyether resins, vinyl formal resins, vinyl acetal resins, cellulose resins, epoxy resins, and urethanes. Resin, polyamide resin, polyimide resin, polyamide imide resin, polyester resin, polyacetal resin, polysulfone resin, polyphenylene sulfide resin, liquid crystal polymer, polyimidazole, polyoxazoline resin, at least one selected from the group consisting of a fluororesin and a silicone resin. Types of hard binders are exemplified.

In the present invention, various additives such as a catalyst, a curing agent, a curing assistant and a modifier which are usually used for these substrates may be used in combination. Further, depending on the purpose of use, a soft substrate, a rubber elastomer, and a hard substrate may be shared.

The mixing ratio of the metal titanate fiber of the present invention and the substrate is the same as that of the curable composition described above.
Parts, preferably in the range of 50 to 1000 parts, are practical. If the amount of the metal titanate fiber is too small, it is not possible to expect characteristics such as dielectric properties or piezoelectricity.On the other hand, if the amount of the substrate is too small, the bonding strength becomes insufficient and the coating performance of the molded body is reduced, and cracks occur. And unsatisfactory strength.

It is preferable that the substrate itself has a high dielectric constant. For example, polyvinylidene fluoride, cyanoethylated polyol, polyvinylphosphabenzene, vinylidene fluoride / trifluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer Preferred examples include coalescence.

As a method for incorporating the metal titanate fiber of the present invention into a substrate, any commonly used disperser, mixer, kneader and the like can be used.
The heating can be performed in any atmosphere such as a heating atmosphere, a cooling atmosphere, a reduced pressure atmosphere, and a specific gas replacement atmosphere. In the present invention, the substrate is used in common with a solvent or a dispersion solvent, and can be used as a solution or as an emulsion, a colloid or other dispersion liquid. Further, a process of including the metal titanate fiber of the present invention in the substrate and / or A solution, a solvent, a dispersing agent, a silane coupling agent, a viscosity modifier, a preservative / preventive agent for improving workability in preparing and / or using the coating composition before and after using the coating composition after the inclusion. Conventional additives such as a binder, a colorant, a plasticizer, a precipitation inhibitor, and a flame retardant aid can be used in combination.

Further, in order to express the performance of the composition of the present invention, an electric field or the like is applied before the preparation and / or use of the coating composition,
It can be electretized.

The present invention is a dielectric or piezoelectric coating composition characterized by containing metal titanate fiber. Since the metal titanate fiber is generally a single crystal fiber, it has a dielectric or piezoelectric property. Since it gives excellent anisotropy and also has a reinforcing effect, it has extremely high industrial applicability.

In the third aspect of the present invention, a composite sheet having a desired form of dielectric or piezoelectric properties is obtained by bonding metal titanate fiber with a binder.

The dielectric or piezoelectric composite sheet of the present invention includes electric and electronic parts such as capacitors and electric wire coverings, and furthermore, electric and electronic elements utilizing temperature change of dielectric constant, piezoelectric effect, remanent polarization and the like. Is applicable to
Sheets and films consisting of only dielectric or piezoelectric portions, sheets and films having a multilayer structure consisting of one or two or more layers each having a dielectric or piezoelectric layer and a mere general insulating layer, Or, a sheet and a film having a multi-layered structure in which a dielectric / piezoelectric layer having different piezoelectric properties and a general insulating layer are each composed of one layer and / or two or more layers, and a design desired by these dielectric / piezoelectric layers and / or general insulating layer And at least one of the dielectric / piezoelectric layers in these sheets and films is composed of a composite sheet containing metal titanate fiber.

In the present invention, the binder is one that imparts sheet moldability by binding metal titanate fiber and other components to be added if necessary and / or binds to a support, There is no limitation, and a thermoplastic or thermosetting water-soluble polymer or hydrophobic polymer can be used freely, and should be selected according to the purpose of use. In general, an organic binder is suitable for the binder of the present invention, but an inorganic binder may be used as long as it has a sheet forming ability and a binding force. Illustrative examples of the binder of the present invention include 1) petrolatum, lanolin, petrotanom, amorphous or low melting point hydrocarbon compounds such as bituminous compounds or derivatives thereof, 2) fatty acids and fatty acids and polyhydric alcohols. Condensates, furthermore, polymers and derivatives thereof, 3) ethylene oxide, homopolymers or copolymers of alkylene oxides such as propylene oxide, 4) rosin, maleated rosin,
Natural resins such as ester gums and derivatives thereof, 5) olefin resins, 6) natural or synthetic rubbers, 7) alkyd resins, 8) acrylic resins, 9) vinyl resins, 10) vinylidene resins, 11)
Vinyl ether resin, 12) polyether resin, 13) vinyl acetal resin, 14) cellulose resin, 15) epoxy resin, 16) urethane resin, 17) polyamide resin, 18)
Polyacetal resin, 19) Polyester resin, 20) Polysulfone resin, 21) Polysulfide resin, 22) Polyimidazole resin, 23) Polyoxazoline, Polyoxazolan resin, 24) Silicon resin, 25) Polymercapto resin, 26) Organosilicon Compounds, organic titanium compounds, organic phosphorus compounds, metal-containing organic compounds such as organic boron compounds,
27) Natural or synthetic compounds such as inorganic binders such as silicates, phosphates and borates, and one or a mixture of two or more of these. These are not only those which have already been made high molecular weight, but also those which express one or a mixture of two or more kinds of raw materials to be made high molecular weight during processing to exhibit a binding force by being made high molecular weight in the presence of light, heat or a catalyst. Can be arbitrarily selected, and the present invention is not limited to only the binders exemplified above.

According to the present invention, a composite sheet having dielectric or piezoelectric properties is obtained by molding into a sheet or a film using a metal titanate fiber and a binder. Can not be specified by the purpose of use, the type of metal titanate fiber and the binder, but if the metal titanate fiber is too small, the dielectric and piezoelectric properties cannot be expected. Insufficient strength of the sheet or film can be expected. Therefore, usually 50 parts to 2000 parts of metal titanate fiber per 100 parts of the binder.
Parts, preferably in the range of 100 to 1000 parts, are practical.

As a method for incorporating the metal titanate fiber in the binder, a dispersion, an emulsion, a solution, or a mixture of the metal titanate fiber and the binder component (the binder or the raw material of the binder) or the binder component may be used. Powder, paste, etc. and, if necessary, diluent,
Mixtures and dispersions obtained by mixing or dispersing a compound composed of various commonly used additives such as a catalyst, a colorant, a silane coupling agent, a dispersant, a plasticizer, an antioxidant, and a filler by a mixer, a disperser, or the like. Get.

The mixture or dispersion is used to form a sheet by an ordinary method. For example, the mixture or dispersion is coated or spread on a surface having releasability to form a sheet. , Paper, cloth made of organic or inorganic fibers, coating or spreading on the surface of a sheet-like support layer such as a resin film, sheet molding, calendering, extrusion molding, etc. As long as the method is used and the processing technique is prepared, blow molding or the like can be used. Further, in order to bring out the performance of the composite sheet of the present invention, an electric field or the like may be applied to the sheet at the time of sheet preparation or after the sheet preparation to form an electret.

When such a mixture or dispersion has an injection molding ability, it can be formed into various shapes, not limited to a sheet, by injection molding by a usual method.

The composite sheet of the present invention may contain a commonly used sheet modifier other than the metal titanate fiber and the binder. The dielectric or piezoelectric properties can be imparted only by the metal titanate fiber of the present invention, but commonly used powdery dielectric ceramic powder, piezoelectric ceramic powder, and inorganic dielectric / piezoelectric compound powder are used in combination. It does not preclude doing anything.

In the composite sheet having dielectric or piezoelectric properties of the present invention, the metal titanate fiber has excellent reinforcing properties, can be oriented as required, can be adjusted for anisotropy, and can be used in a usual manner. Under the use environment, physical and chemical changes such as oxidation hardly occur and heat resistance is excellent, so a composite sheet with stable dielectric or piezoelectric properties can be obtained.
It has extremely high industrial utility.

The composite sheet comprising an elastic material as a binder and lead zirconate titanate whiskers as metal titanate fibers had particularly excellent piezoelectricity.

Although pyroelectricity is not mentioned throughout the present invention, a composition having pyroelectricity is expected when a metal titanate whisker having good pyroelectricity, for example, a lead titanate whisker is used. it can.

[0051]

Next, the features of the present invention will be described in more detail with reference to examples.

Example 1 A polypropylene resin (Sumitomo Noblen H501, manufactured by Sumitomo Chemical Co., Ltd.) and barium titanate whisker (Otsuka Chemical Co., Ltd., average fiber length: 14.2 μm, fiber diameter: 0.3 to 0.5 μm) 65/35, 60/4 respectively
Weigh so that the ratio of 0, 40/60, 30/70,
After sufficiently drying at 110 ° C., the polypropylene resin was melted for 5 minutes using Labo Plastmill (manufactured by Toyo Seiki Co., Ltd.).
And kneading for 5 minutes at a temperature of 175 ° C., respectively, and the obtained compound was charged into a compression molding machine (manufactured by Shinto Metal Industry Co., Ltd.), and 190 ° C., a gauge pressure of 50 kgf / cm ^2.
The sample was heated and pressed to prepare a flat plate sample, and the dielectric constant of each sample was measured.

The dielectric constant (ε) is measured according to JIS K 691
Measurement frequency 1KH using LCR meter conforming to 1.
z, and the voltage between samples was 1 V. The difference from the comparative example described later was obvious, and a difference in the dielectric constant of about twice or more was observed (FIG. 1).

Comparative Example 1 A barium titanate whisker of Example 1 was replaced with a commercially available barium titanate powder (BT303, manufactured by Fuji Titanium Co., Ltd.). A sample of a similar flat plate was prepared, and each dielectric constant was measured.

FIG. 1 clearly shows that the composition of the present invention has excellent dielectric properties.

Example 2 Polyacetal resin (Duracon, manufactured by Polyplastics Co., Ltd.) and NBR (JSRP, manufactured by Nippon Synthetic Rubber Co., Ltd.)
(N30A, CN content 35%) is kneaded while applying stress while mixing little by little at a temperature of 190 ° C using a heating roll so as to adjust the weight ratio to 60/40.
When mixed well, lead zirconate titanate whiskers (manufactured by Otsuka Chemical Co., Ltd., average fiber length: 12 μm, fiber diameter: 0.5 to 0.6 μm) were polymer alloy / whisker = 35 / weight ratio with respect to the above polymer alloy. The mixture was uniformly mixed while being added little by little to 65, and then formed into a 50 μm thick film using a hot press. While heating the molded article to about 60 ° C. to impart piezoelectricity to the film, a DC electric field having an electric field strength of 200 KV / cm is applied from the front and back of the molded article for 1 hour as it is, and the film is rapidly cooled. The piezoelectric constant (d ₃₁ ) of the resulting piezoelectric material is 130.5 × 10 ⁻⁸
(CGS esu). For reference, instead of lead zirconate titanate whiskers, lead zirconate titanate (reagent class 1 manufactured by Hanoi Chemicals Co., Ltd.) known as a general piezoelectric ceramic powder was used, and a film having a thickness of 50 μm was similarly heated and pressed. Is formed into an electret, and its piezoelectric constant (d ₃₁ ) is 50.2 × 10 ⁻⁸ (CGS
esu), which clearly shows that the composition of the present invention has excellent piezoelectric properties. In addition, a silver vapor-deposited film vacuum-deposited on both surfaces of the film was used as an electrode at the time of electretization and measurement of a piezoelectric constant.

Example 3 Butadiene was polymerized by using hydrogen peroxide as a catalyst to obtain a liquid polybutadiene polyol having an average molecular weight of 2,800, an OH group of 0.85 meq / g, 1,2 bonds 21%, and 1,4 bonds 79%. The obtained polybutadiene polyol 100
Parts, dried barium titanate whiskers (600 parts) and dibutyltin dilaurate (0.1 part) were mixed with a three-roll paint roll. To 100 parts of this mixture, 1.2 parts of tolylene diisocyanate was added, and at 120 ° C. for 1 hour,
In-press curing was performed. The electrical properties of the cured product thus obtained were measured according to JIS K 6911, and the dielectric constant was 24 (1 KHz, 20 ° C.) and 22 (1
KHz, 120 ° C.), dielectric loss tangent (tan δ) is 0.01
3 and 0.003. As a reference, a cured product was obtained in the same manner as in Example 3 except that the same amount of a commercially available barium titanate powder (BT303, manufactured by Fuji Titanium Co., Ltd.) was added instead of the barium titanate whisker. , Permittivity is 12 (1 KHz, 20 ° C.), 10 (1 KHz
Hz, 120 ° C.), and the dielectric loss tangent (tan δ) is 0.
02 and 0.005.

[0058]

According to the composition having dielectric or piezoelectric properties of the present invention, the metal titanate fiber has excellent reinforcing properties and exhibits highly anisotropic dielectric / piezoelectric properties by being oriented as required. Therefore, it can be used in place of a conventional polymer dielectric / piezoelectric material or polymer composite dielectric / piezoelectric material, and has extremely high industrial applicability.

[Brief description of the drawings]

FIG. 1 shows the relationship between the added amount of barium titanate whisker and barium titanate powder and the dielectric constant of the molded articles (plates) obtained in Example 1 and Comparative Example 1, respectively. .

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Minoru Aki 463 Kagasuno, Kawauchi-machi, Tokushima City, Tokushima Prefecture Inside the Tokushima Research Laboratory, Otsuka Chemical Co., Ltd. No. 27 Otsuka Chemical Co., Ltd. (56) References JP-A-56-162403 (JP, A) JP-A-57-188462 (JP, A) JP-A-62-274502 (JP, A) JP-A-60 −218703 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C01G 23/00 H01B 3/00 H01G 4/20

Claims (3)

(57) [Claims] 1. The general formula MO · n (Ti, X) O ₂ (wherein M is a metal element of a single or a plurality of divalent ions, X
Is a zero or zirconium, and n is a real number) 1 to 1000 μm in fiber length and 0.01 to 10 μm in fiber diameter
A dielectric or piezoelectric composition consisting of a metal titanate fiber (except for lead zirconate titanate whiskers) and a binder , the orientation direction of the fiber being constant
A molded article formed by a molding method that does not . 2. The metal titanate fiber has a fiber length of 2 to 50 μm.
m, a metal titanate fiber having a fiber diameter of 0.1 to 2 μm.
The molded article according to claim 1 . 3. A gold titanate based on 100 parts by weight of a binder.
The salt fiber according to claim 1 or 50 to 1000 parts by weight.
The molded article according to claim 2 .